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The unexpected but facile preparation of the silver salt of the least coordinating [(RO)3Al-F-Al(OR)3]- anion (R=C(CF3)3) by reaction of Ag[Al(OR)4] with one equivalent of PCl3 is described. The mechanism of the formation of Ag[(RO)3Al-F-Al(OR)3] is explained based on the available experimental data as well as on quantum chemical calculations with the inclusion of entropy and COSMO solvation enthalpies. The crystal structures of (RO)3Al<--OC4H8, Cs+[(RO)2(Me)Al-F-Al(Me)(OR)2]-, Ag(CH2Cl2)3+[(RO)3Al-F-Al(OR)3]- and Ag(eta2-P4)2+[(RO)3Al-F-Al(OR)3]- are described. From the collected data it will be shown that the [(RO)3Al-F-Al(OR)3]- anion is the least coordinating anion currently known. With respect to the fluoride ion affinity of two parent Lewis acids Al(OR)3 of 685 kJ mol(-1), the ligand affinity (441 kJ mol(-1)), the proton and copper decomposition reactions (-983 and -297 kJ mol(-1)) as well as HOMO level and HOMO-LUMO gap and in comparison with [Sb4F21]-, [Sb(OTeF5)6]-, [Al(OR)4]- as well as [B(R(F))4]- (R(F)=CF3 or C6F5) the [(RO)3Al-F-Al(OR)3]- anion is among the best weakly coordinating anions (WCAs) according to each value. In contrast to most of the other cited anions, the [(RO)3Al-F-Al(OR)3] anion is available by a simple preparation in conventional inorganic laboratories. The least coordinating character of this anion was employed to clarify the question of the ground state geometry of the Ag(eta2-P4)2+ cation (D(2h), D(2) or D(2d)?). In agreement with computational data and NMR spectra it could be shown that the rotation along the Ag-(P-P-centroid) vector has no barrier and that the structure adopted in the solid state depends on packing effects which lead to an almost D(2h) symmetric Ag(eta2-P4)2+ cation (0 to 10.6 degrees torsion) for the more symmetrical [Al(OR)4]- anion, but to a D2 symmetric Ag(eta2-P4)2+ cation with a 44 degrees twist angle of the two AgP2 planes for the less symmetrical [(RO)3Al-F-Al(OR)3]- anion. This implies that silver back bonding, suggested by quantum chemical population analyses to be of importance, is only weak.
Based on measurements of relative phase and frequency coordination of time-space distributed firing of single neurons and neuron assemblies in the human nervous system, the concept of coordination dynamics to describe the integrative functions of the human central nervous system (CNS) and the finding of neurogenesis in the human CNS, the coordination dynamic therapy has been developed with which it is possible to repair the lesioned or malfunctioning human CNS. With the developed coordination dynamic recording method the organization (the coordination dynamics) of the CNS can be measured on-line non-invasively. By measuring the present coordination dynamics at different times with ongoing coordination dynamic therapy when exercising on a special coordination dynamic therapy device, the progress in re-organization and repair of the lesioned CNS can be quantified. In this paper it is reported that in 8 patients following stroke the lesioned CNS could partly be repaired by coordination dynamic therapy. The repair was quantified by the improvement of walking, hand function and the direct measurement of CNS organization (the coordination dynamics). In 4 patients the improvement of CNS organization (coordinations dynamics) was 70 +/- 14% within 3 months of therapy. In a patient where the intensive coordination dynamic therapy (at least 4 hours therapy with more than 15,000 coordinated movements per day) lasted longer than one year, also the difficult repairable hand functions could substantially be improved. It is shown that in the healthy CNS of the author the coordination dynamics improved in the short-term memory by 20% within 10 min and in a stroke patient by 70% within 30 min, when exercising on the special coordination dynamic therapy device. As in other learning therapies (school) it is believed, that by repeated learning of movements, vegetative and higher mental functions in the short-term memory, the learned CNS functions will also go into the long-term memory, which means the CNS has been reorganized. Improvements in the short-term memory are used to motivate the patient to perform a therapy.
BACKGROUND: Children with Developmental Coordination Disorder (DCD) have difficulties producing stable rhythmic bimanual coordination patterns in comparison with age-related peers. Rhythmic coordination of non-homologous limbs (e.g. hand and foot) is even more difficult to perform because of mechanical differences between the limbs. The aim of the present study is to investigate the stability of hand-foot coordination patterns of children with DCD. METHODS: Ten children with DCD (mean age 7.0 years, SD 1.1 years) and 16 control children (mean age 7.4 years, SD 1.3 years) participated in the study. They were asked to perform in-phase or anti-phase tapping movements in three different interlimb coordination combinations: (1) hand-hand (homologous), (2) hand-foot same body side (ipsilateral), and (3) hand-foot different body side (contralateral). Coordination stability was measured by the variability of the relative phase between the limbs under a 'steady state' (preferred) frequency condition, and by the critical frequency (i.e. the point at which loss of pattern stability was observed) in a condition in which the movement frequency was 'scaled' up (only anti-phase tapping). RESULTS: Coordination patterns of children in the DCD group were less stable in all three limb combinations compared with controls. Further, hand-foot coordination patterns were less stable than hand-hand coordination patterns. With regard to hand-foot coordination, ipsilateral patterns were equally stable compared with contralateral patterns in the in-phase task, but less stable in the anti-phase task. No differential effects were found between the DCD and control groups across the different limb combinations, except for steady-state anti-phase coordination in the ipsilateral limb condition. This effect was due to a relatively good performance of the control children in this condition in comparison with the other limb combination conditions. CONCLUSIONS: Children with DCD have difficulties producing stable rhythmic hand-foot coordination patterns compared with control children.
To examine the porphyrin-core expansion and the conformational variations induced by a change in the coordination sphere of nickel(II) from four-coordinate, low-spin (S = 0) to six-coordinate, high-spin (S = 1), several nickel(II) derivatives of tetraphenylporphyrins, substituted in their beta-pyrrole positions with electron-withdrawing groups, were isolated and studied by X-ray crystallography. The four-coordinate nickel(II) complex studied, Ni(TPP(Br)(4)(CN)(4)) (1), is a derivative of the antipodal beta-pyrrole brominated and cyanated macrocycle, 2,3,12,13-tetrabromo-7,8,17,18-tetracyano-5,10,15,20-tetraphenylporphyrin. One of the six-coordinate species is the bis-pyridine nickel(II) adduct, Ni(TPP(Br)(4)(CN)(4))(py)(2) (2), of this antipodal beta-pyrrole brominated and cyanated ring, whereas the second six-coordinate complex is the bis-1-methylimidazole nickel(II) adduct, Ni(TPP(CN)(4))(1-MeIm)(2) (3), of the antipodal tetracyanated macrocycle, 7,8,17,18-tetracyano-5,10,15,20-tetraphenylporphyrin. This study confirms that, upon conversion of a four-coordinate, low-spin nickel(II) derivative of a beta-pyrrole-substituted tetraphenylporphyrin into a six-coordinate, high-spin complex, a radial expansion of the porphyrin core also takes place. This radial expansion flattens the porphyrin core, inducing more planarity in the conformations of the six-coordinate nickel(II) porphyrin species. The X-ray structure of 1 reveals an average Ni-N(p) bond distance of 1.920(2) Å, similar to that present in tetragonal Ni(OEP) [(Ni-N(p))(av) = 1.929(3) Å], the ruffled low-spin nickel(II) (S = 0) porphyrin derivative, and many other low-spin nickel(II) complexes of distorted porphyrins. The conformation of the macrocycle present in 1 is severely saddle-shaped with a small ruffling and a minor doming. The structures of 2 and 3 indicate a clear expansion of the porphyrin cores with two sets of (Ni-N(p))(av) bond lengths of 2.040(2) and 2.073(2) Å in 2 and 2.037(2) and 2.068(2) Å in 3, which differ significantly from the average Ni-N(p) distance occurring in 1. Relative to the conformation of the porphyrin ring present in 1, the high-spin complex 2 is less saddle-shaped, but more ruffled. In 3, in which only two opposite pyrrole rings of the porphyrin are substituted by cyano groups, the macrocycle adopts a slightly waved conformation. Crystal data: Ni(TPP(Br)(4)(CN)(4)).2.5(1,2-Cl(2)C(2)H(4)), [1.2.5(1,2-Cl(2)C(2)H(4))], triclinic, space group P&onemacr;, a = 13.741(1) Å, b = 14.029(2) Å, c = 15.201(2) Å, alpha = 89.037(9) degrees, beta = 70.829(8) degrees, gamma = 67.607(8) degrees, V = 2539.4(5) Å(3), T = 20 degrees C, Z = 2, R(F)() = 0.047 and R(wF) = 0.067 based on 5341 reflections with I > 3sigma(I); Ni(TPP(Br)(4)(CN)(4))(py)(2).2.5(1,2-Cl(2)C(2)H(4)), [2.2.5(1,2-Cl(2)C(2)H(4))], triclinic, space group P&onemacr;, a = 11.9472(9) Å, b = 14.3651(7) Å, c = 19.556(1) Å, alpha = 87.049(5) degrees, beta = 73.181(6) degrees, gamma = 70.613(5) degrees, V = 3026.8(4) Å(3), T = 173 K, Z = 2, R(F)() = 0.036, R(wF) = 0.041 based on 6846 reflections with I > 3sigma(I); Ni(TPP(CN)(4))(1-MeIm)(2).2CH(2)Cl(2), [3.2(CH(2)Cl(2))], monoclinic, space group C2/c, a = 26.804(8) Å, b = 10.948(3) Å, c = 19.453(5) Å, beta = 113.13(2) degrees, V = 5251.5 Å(3), T = 20 degrees C, Z = 4, R(F)() = 0.047, R(wF) = 0.067 based on 4384 reflections with I > 3sigma(I).
The three-dimensional video analysis of human motion commonly utilises automated image processing and digitisation processes to produce real-time unidentified two-dimensional coordinate data of segmental markers. In what can be a time-consuming process the two-dimensional data are then identified and tracked to produce three-dimensional coordinates. This paper presents an approach to the automated reproduction of three-dimensional coordinates from two-dimensional coordinates data. Conjugate imaging techniques were utilised in the development of four criterion measures for determining the validity of conjugate (corresponding) image points. An algorithm based on the criterion measures was then developed for the automated reproduction of three dimensional coordinates from camera image coordinate data. The algorithm was tested with a 55 point marker system viewed in four video cameras (digitisation error approx. 0.2%, lab point separation > or = 6 cm). The success of the algorithm was dependent on the closeness of markers, the accuracy of the photogrammetric system, and the number of markers visible in two camera images. The present research has developed techniques based on conjugate imagery for the automated reproduction of three-dimensional coordinates from two-dimensional data, and provided a bases for further development of automated three-dimensional tracking.
Neuronal organisms express their function, such as a movement, by multicomponental actions. Thus, the problem of how the central nervous system (CNS) coordinates the elements of a single action is fundamental to our understanding of brain function. Coordinated activation of multijointed "limbs" has also become an acute problem in modern multivariable control theory and engineering, such as robotics. Thus, a coherent interdisciplinary approach is expected, one that arrives at concepts and formalisms applicable to this problem both in living and man-made organisms. By treating coordination with coordinates, tensor network theory of the CNS, which explains transformations through the neuronal networks of natural non-orthogonal coordinates that are intrinsic to living organisms, may successfully integrate the diverse approaches to this general problem. A link between tensor network theory of the CNS and multivariable control engineering can be established if the latter is formulated in generalized non-orthogonal coordinates, rather than in conventional Cartesian expressions. In general terms, the problem of coordinating an overcomplete (more than necessary) number of components of an action can be resolved by a three-step tensorial scheme. A key operation is a covariant-to-contravariant transformation executed by the Moore-Penrose generalized inverse when, in an overcomplete manifold, the covariant metric tensor is singular. In the neuronal organization of the CNS, it is assumed that the cerebellum plays this role of acting as a contravariant metric. A quantitative example is also provided, in order to demonstrate the viability of the numerical and network-implementations.
Application of in situ X-ray absorption near-edge spectroscopy (XANES) at the Al K-edge provides unique insight into the flexibilty of the aluminum coordinations in zeolites as a function of treatment or during true reaction conditions. A unique, previously not observed, pre-edge feature is detected in zeolites H-Mordenite and steamed and unsteamed H-Beta at temperatures above 675 K. Spectra simulations using the full multiple scattering code Feff8 identify the unique pre-edge feature as three-coordinate aluminum. The amount of three-fold coordinated aluminum is a function of temperature and pretreatment of a zeolite: a steamed zeolite Beta contains more three-coordinate aluminum than an unsteamed sample. No clear differences between zeolites H-Mordenite and H-Beta were observed. Octahedrally coordinated aluminum forms in zeolites H-Mordenite and H-Beta at room temperature in a stream of wet helium. This octahedrally coordinated aluminum is unstable at temperatures higher than 395 K, where it quantitatively reverts to the tetrahedral coordination.
Intra- and interpersonal interlimb coordination of pendulums swung from the wrist was investigated. For both kinds of coordination, the steady state and breakdown of bimanual rhythmic coordination as indexed by the time series of the relative phase angle phi were studied under the manipulation of coordination mode, frequency of oscillation, and the difference in the eigenfrequencies (preferred tempos) of the individual oscillating limbs. The properties observed for both intra- and interpersonal coordination were those predicted by a dynamical model of rhythmic coordination that considers the coordinated limbs coupled to be nonlinear oscillators. Using a regression method, the coupling strengths of the coupled system were recovered. As predicted by the dynamical model, the strength of the dynamic was generally greater for the in-phase than the anti-phase mode and decreased with increasing frequency. Further, the strength of the interpersonal interlimb coupling was weaker than that of intrapersonal interlimb coupling.
[Cu(2,9-dimethyl-1,10-phenanthroline)(2)](2+) and [Cu(6,6'-dimethyl-2,2'-bipyridine)(2)](2+/+) complexes with no coordinated solvent molecule were synthesized and the crystal structures were analyzed: the coordination geometry around the Cu(i) center was in the D(2d) symmetry while a D(2) structure was observed for the four-coordinate Cu(ii) complexes. Coordination of a water or an acetonitrile molecule was found in the trigonal plane of the five-coordinate Cu(ii) complex in the Tbp(trigonal bipyramidal) structure. Spectrophotometric analyses revealed that the D(2) structure of the Cu(ii) complex was retained in nitromethane, although a five-coordinate Tbp species (green in color), was readily formed upon dissolution of the solid (reddish brown) in acetonitrile. The electron self-exchange reaction between D(2d)-Cu(I) and D(2)-Cu(II), observed by the NMR method, was very rapid with k(ex)=(1.1 +/- 0.2) x 10(5) kg mol(-1) s(-1) at 25 degrees C (DeltaH*= 15.6 +/- 1.3 kJ mol(-1) and DeltaS*=-96 +/- 4 J mol(-1) K(-1)), which was more than 10 times larger than that reported for the self-exchange reaction between D(2d)-Cu(I) and Tbp-Cu(II) in acetonitrile. The cross reduction reactions of D(2)-Cu(ii) by ferrocene and decamethylferrocene in nitromethane exhibited a completely gated behavior, while the oxidation reaction of D(2d)-Cu(i) by [Ni(1,4,7-triazacyclononane)(2)](3+) in nitromethane estimated an identically large self-exchange rate constant to that directly obtained by the NMR method. The electron self-exchange rate constant estimated from the oxidation cross reaction in 50% v/v acetonitrile-nitromethane mixture was 10 times smaller than that observed in pure nitromethane. On the basis of the Principle of the Least Motion (PLM) and the Symmetry Rules, it was concluded that gated behaviors observed for the reduction reactions of the five-coordinate Cu(ii)-polypyridine complexes are related to the high-energy C(2v)--> D(2d) conformational change around Cu(ii), and that the electron self-exchange reactions of the Cu(ii)/(i) couples are always adiabatic through the C(2v) structures for both Cu(ii) and Cu(i) since the conformational changes between D(2d), D(2) and C(2v) structures for Cu(i) as well as the conformational change between Tbp and C(2v) structures for Cu(ii) are symmetry-allowed. The completely gated behavior observed for the reduction reactions of D(2)-Cu(ii) species in nitromethane was attributed to the very slow conformational change from the ground-state D(2) to the entatic D(2d) structure that is symmetry-forbidden for d(9) metal complexes: the very slow back reaction, the forbidden conformational change from entatic D(2d) to the ground-state D(2) structure, ensures that the rate of the reduction reaction is independent of the concentration of the reducing reagent.
The processes which develop to coordinate eye and hand movements in response to motion of a visual target were studied in young children and adults. We have shown that functional maturation of the coordination control between eye and hand takes place as a result of training. We observed, in the trained child and in the adult, that when the hand is used either as a target or to track a visual target, the dynamic characteristics of the smooth pursuit system are markedly improved: the eye to target delay is decreased from 150 ms in eye alone tracking to 30 ms, and smooth pursuit maximum velocity is increased by 100%. Coordination signals between arm and eye motor systems may be responsible for smooth pursuit eye movements which occur during self-tracking of hand or finger in darkness. These signals may also account for the higher velocity smooth pursuit eye movements and the shortened tracking delay when the hand is used as a target, as well as for the synkinetic eye-arm motions observed at the early stage of oculo-manual tracking training in children. We propose a model to describe the interaction which develops between two systems involved in the execution of a common sensorimotor task. The model applies to the visuo-oculo-manual tracking system, but it may be generalized to other coordinated systems. According to our definition, coordination control results from the reciprocal transfer of sensory and motor information between two or more systems involved in the execution of single, goal-directed or conjugate actions. This control, originating in one or more highly specialized structures of the central nervous system, combines with the control processes normally operating in each system. Our model relies on two essential notions which describe the dynamic and static aspects of coordination control: timing and mutual coupling.
The coordination dynamics of learning and transfer were studied in a single limb multijoint task requiring rhythmic elbow and wrist motions. Participants were required to learn a continuous 90 degrees relative phase pattern between the elbow and wrist such that an angle-angle plot of elbow and wrist motion produced a circle with a diameter of 80 degrees. Joint motion was restricted to elbow and wrist flexion-extension on the sagittal plane and the to-be-learned 90 degrees relative phase pattern was always practiced with the learning arm supine. Cycling frequency was controlled by a pacing metronome set at 0.75 Hz. Issues regarding effector-independent and effector-specific transfer were addressed with three transfer conditions: (1). learning arm prone (LP), (2). non-learning arm supine (NS), and (3). non-learning arm prone (NP). Four subjects learned the required relative phase (90 degrees ) and amplitude (80 degrees ) pattern with their dominant arm and four with their non-dominant arm. The experiment produced three main findings with regard to elbow-wrist control processes: First, seven of eight participants spontaneously produced a wrist-lagging coordination pattern (wrist motion lagged elbow motion) in learning to produce a continuous relative phase pattern of 90 degrees between the elbow and wrist. The wrist-lagging pattern may emerge as a result of the central nervous system exploiting the transfer of angular momentum from the elbow to the wrist as the elbow rotates up and down. The influence of interactive torque on elbow-wrist coordination represents an important mechanical constraint on the selection of intralimb coordination strategies during learning. The transfer conditions revealed that this mechanical constraint was effector-independent with regard to ipsilateral limb transfer (LP) and contralateral limb transfer (NS and NP). Second, consistent transfer of the learned relative phase pattern across ipsilateral and contralateral conditions demonstrates an effector-independent representation for this control variable. The effector-independent and effector-specific nature of joint amplitude transfer was dependent to some degree on learning arm, dominant or non-dominant, and the amount of practice, 1 day versus 5 days. Third, learning of the required 90 degrees relative phase pattern may be characterized as a phase transition leading to the formation of a stable attractor in the elbow-wrist coordination landscape. The above findings are discussed with respect to motor programming and coordination dynamic viewpoints on effector-independent and effector-specific aspects of motor equivalence.
Previous studies have identified motor deficits on the ipsilesional side of patients recovering from a cerebro-vascular accident (CVA), including deficits in interlimb coordination. In the present study, unilateral stroke patients and a control group of healthy age-matched controls performed nonisodirectional coordination of the ipsilateral limbs across two days of practice with feedback. Findings revealed that control subjects were already quite successful at initiation of practice but further improved the coordination pattern across both days. The group of CVA patients also showed some improvement but problems with coordination of the ipsilateral limb segments persisted across practice. Variability in both timing and amplitude of both limb segments did improve with practice in both groups but these measures remained significantly higher in the CVA patients. Even though isodirectional and nonisodirectional coordination of the ipsilateral limb segments are normally considered to be part of the intrinsic motor repertoire, the present study suggests that nonisodirectional ipsilesional limb coordination poses considerable difficulties for CVA patients that are not easily overcome with feedback-assisted practice.
The silver(I) coordination chemistry of 2,6-diarylpyrazines is reported. Discrete coordination complexes and two-dimensional coordination networks were characterized. The substitution pattern on the pendant aryl groups controlled the type of coordination chemistry involved. Thus, o-methyl-substituted aryl groups held the aryl groups orthogonal to the central pyrazine ring, opening the "hindered" nitrogen atoms to complexation, and polymeric networks were characterized. In the absence of the o-methyl groups, discrete coordination complexes were characterized. Thus, a dimeric 2:1 ligand-silver(I) complex was isolated and characterized on reaction of 2,6-bis(3',5'-dimethylphenyl)pyrazine with silver(I) trifluoroacetate in acetonitrile solvent, while a 2:2 complex was isolated from dichloromethane solvent. Two trifluoroacetate ligands bridge two silver cations in both complexes. Reaction of the same pyrazine ligand with silver(I) tetrafluoroborate yielded a discrete 2:1 complex. A 2:1 complex was isolated on reaction of 2,6-diphenylpyrazine with silver(I) nitrate. These complexes were interlinked by weakly coordinating nitrate anions to form interwoven one-dimensional ribbons. Two-dimensional networks were obtained on reaction of silver(I) trifluoroacetate with either 2,6-bis(2',6'-dimethylphenyl)pyrazine or 2-(2',6'-dimethylphenyl)-6-(3',5'-dimethylphenyl)pyrazine. The networks comprised pyrazine-silver(I) strands cross-linked with complex bridged silver(I) trifluoroacetates.
The novel phosphinite PPh(2)(3-OCH(2)C(5)H(4)N) (1) has been synthesized, and its coordination properties to Ag(I) have been studied. When reacted in a 1:1 ratio with Ag(I), coordination polymers with different coordination numbers about the Ag are found depending on the anion. For PPh(2)(3-OCH(2)C(5)H(4)N)AgBF(4) (2), a two-coordinate Ag is observed with a P-Ag-N angle of 167 degrees. Mixed three and four coordination about Ag is observed for PPh(2)(3-OCH(2)C(5)H(4)N)AgOTf (3), and for the trifluoroacetate derivative, PPh(2)(3-OCH(2)C(5)H(4)N)Agtfa (4), only a four-coordinate Ag is produced. X-ray crystal-structure determinations for compounds 2-4 have been carried out. The X-ray structures show a wide range of Ag-Ag distances in the polymers, which are dependent on the conformation of the bridging ligand.
Five-coordinate metal complex ions of the type [ML](2+) [where M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and L= 1,9-bis(2-pyridyl)-2,5,8-triazanonane (DIEN-(pyr)(2)) and 1,9-bis(2-imidazolyl)-2,5,8-triazanonane (DIEN-(imi)(2)] have been reacted with acetonitrile in the gas phase using a modified quadrupole ion trap mass spectrometer. The kinetics and thermodynamics of these reactions show that the reactivity of these complexes is affected by metal electronic structure and falls into three groups: Mn(II) and Ni(II) complexes are the most reactive, Fe(II) and Co(II) complexes exhibit intermediate reactivity, and Cu(II) and Zn(II) complexes are the least reactive. To help explain the experimental trends in reactivity, theoretical calculations have been used. Due to the relatively large size of the metal complexes involved, we have utilized a two-layered ONIOM method to perform geometry optimizations and single point energy calculations for the [ML](2+) and [ML + CH(3)CN](2+) systems. The calculations show that the reactant five-coordinate complexes ([ML](2+)) exhibit structures that are slightly distorted trigonal bipyramidal geometries, while the six-coordinate complexes ([ML + CH(3)CN](2+)) have geometries that are close to octahedral. The Delta G values obtained from the ONIOM calculations roughly agree with the experimental data, but the calculations fail to completely explain the trends for the different metal complexes. The failure to consider all possible isomers as well as adequately represent pi-d interactions for the metal complexes is the likely cause of this discrepancy. Using the angular overlap model (AOM) to obtain molecular orbital stabilization energies (MOSE) also fails to reproduce the experimental trends when only sigma interactions are considered but succeeds in explaining the trends when pi interactions are taken into account. These results indicate that the pi-donor character of the CH(3)CN plays a subtle, yet important, role in controlling the reactivity of these five-coordinate complexes. Also, the AOM calculations are consistent with the experimental data when the [ML](2+) complexes have high-spin trigonal bipyramidal configurations. Generally, these results suggest that ion-molecule reactions can be very sensitive to metal complex coordination geometry and thus may have some promise for providing gas-phase coordination structure.
The coordination or ion pairing of the hydrogen-bonded anions H(CF3CO2)2- and H(CH3SO3)2- to NEt4+, Li+, Cu+, and/or Cu2+ was investigated. The structure of [Cu2(H(CH3SO3)2)4]n consists of centrosymmetric dimeric moieties that contain two homoconjugated (CH3SO2O-H...OSO2CH3)- anions per Cu2+ ion, forming typical Jahn-Teller tetragonally elongated CuO6 coordination spheres. The oxygen atoms involved in the nearly linear O-H...O hydrogen bonds (O...O approximately 2.62 A) are not coordinated to the Cu2+ ions. The structure of Cu2(CO)2(H(CF3-CO2)2)2 consists of pseudo-C2-symmetric dimers that contain one homoconjugated (CF3COO-H...OCOCF3)- anion per Cu+ ion, forming highly distorted tetrahedral Cu(CO)O3 coordination spheres. Three of the four oxygen atoms in each hydrogen-bonded H(CF3CO2)2- anion are coordinated to the Cu+ ions, including one of the oxygen atoms in each O-H...O hydrogen bond (O...O approximately 2.62 A). Infrared spectra (v(CO) values) of Cu(CO)(CF3CO2) or Cu(CO)(CH3SO3) dissolved in acetonitrile or benzene, with and without added CF3COOH or CH3SO3H, respectively, demonstrate that HA2- anions involving carboxylates or sulfonates are more weakly coordinating than the parent anions RCO2- and RSO3-. Direct current conductivities of THF solutions of Li(CF3CO2) containing varying concentrations of added CF3COOH further demonstrate that Li+ and NEt4+ ion pair much more weakly with H(CF3CO2)2- than with CF3CO2-.
The dicyanodicarbonyliron(II) thiolate complexes trans,cis-[(CN)(2)(CO)(2)Fe(S,S-C-R)](-) (R = OEt (2), N(Et)(2) (3)) were prepared by the reaction of [Na][S-C(S)-R] and [Fe(CN)(2)(CO)(3)(Br)](-) (1). Complex 1 was obtained from oxidative addition of cyanogen bromide to [Fe(CN)(CO)(4)](-). In a similar fashion, reaction of complex 1 with [Na][S,O-C(5)H(4)N], and [Na][S,N-C(5)H(4)] produced the six-coordinate trans,cis-[(CN)(2)(CO)(2)Fe(S,O-C(5)H(4)N)](-) (6) and trans,cis-[(CN)(2)(CO)(2)Fe(S,N-C(5)H(4))](-) (7) individually. Photolysis of tetrahydrofuran (THF) solution of complexes 2, 3, and 7 under CO led to formation of the coordinatively unsaturated iron(II) dicyanocarbonyl thiolate compounds [(CN)(2)(CO)Fe(S,S-C-R)](-) (R = OEt (4), N(Et)(2) (5)) and [(CN)(2)(CO)Fe(S,N-C(5)H(4))](-) (8), respectively. The IR v(CN) stretching frequencies and patterns of complexes 4, 5, and 8 have unambiguously identified two CN(-) ligands occupying cis positions. In addition, density functional theory calculations suggest that the architecture of five-coordinate complexes 4, 5, and 8 with a vacant site trans to the CO ligand and two CN(-) ligands occupying cis positions serves as a conformational preference. Complexes 2, 3, and 7 were reobtained when the THF solution of complexes 4, 5, and 8 were exposed to CO atmosphere at 25 degrees C individually. Obviously, CO ligand can be reversibly bound to the Fe(II) site in these model compounds. Isotopic shift experiments demonstrated the lability of carbonyl ligands of complexes 2, 3, 4, 5, 7, and 8. Complexes [(CN)(2)(CO)Fe(S,S-C-R)](-) and NiA/NiC states [NiFe] hydrogenases from D. gigas exhibit a similar one-band pattern in the v(CO) region and two-band pattern in the v(CN) region individually, but in different positions, which may be accounted for by the distinct electronic effects between [S,S-C-R](-) and cysteine ligands. Also, the facile formations of five-coordinate complexes 4, 5, and 8 imply that the strong sigma-donor, weak pi-acceptor CN(-) ligands play a key role in creating/stabilizing five-coordinate iron(II) [(CN)(2)(CO)Fe(S,S-C-R)](-) complexes with a vacant coordination site trans to the CO ligand.