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Yi-Hong Ding

Publications and source records attributed to Yi-Hong Ding.

At least 19 recordsLinked to original sources
PubMed2007

Design of sandwichlike complexes based on the planar tetracoordinate carbon unit CAl4(2-).

Ever being a large curiosity, a series of simple "planar tetracoordinate carbon (ptC)" molecules have been recently characterized by experiments. Incorporation of such exotic ptC units into the assembled molecular materials, which will bridge the isolated clusters in molecular beams and the potential solid materials, is very challenging. In this paper, we described the first attempt on how to assemble the fewest-number ptC unit CAl42- into molecular materials in sandwich forms on the basis of the density functional theory calculations on a series of model compounds [D(CAl4)M]q- as well as the saturated compounds [D(CAl4)Mn] ((D = CAl42-, Cp-(C5H5-); M = Li, Na, K, Be, Mg, Ca). For M = Li, Be, Mg, and Ca, the ptC unit CAl42- can only be assembled in our newly proposed "heterodecked sandwich" scheme (e.g., [Cp(CAl4)M]q- (M = Li, Na, K, q = 2; M = Be, Mg, Ca, q = 1)) so as to avoid cluster fusion. For M = Na and K, the ptC unit CAl42- can be assembled in both the traditional "homodecked sandwich" [(CAl4)2M]q- (M = Li, Na, K, q = 3; M = Be, Mg, Ca, q = 2) and the novel heterodecked sandwich schemes. Moreover, the counterions were found to have an important role in determining the type of the ground structures for the homodecked sandwich. Various assembled species in extended frameworks were designed. Notably, among all the designed sandwich species, the ptC unit CAl42- generally prefers to interact with the partner deck at the side (Al-Al bond) or corner (Al atom) site. This has not been reported in the sandwich complexes on the basis of the known decks such as Cp-, P5-, N42-, and Al42-, for which only the traditional face-face interaction type was considered. Our results for the first time showed that the ptC unit CAl42- can act as a new type of "superatom". The present results are expected to enrich the flat carbon chemistry, superatom chemistry, metallocenes, and combinational chemistry.

Journal Article↗
PubMed2007

Sandwich-like compounds based on the all-metal aromatic unit Al(4)2- and the main-group metals M (M=Li, Na, K, Be, Mg, Ca).

Inspired by the pioneering experimental characterisation of the all-metal aromatic unit Al(4)2- in the bimetallic molecules MAl4- (M=Li, Na, Cu) and by the very recent theoretical design of sandwich-type transition-metal complexes [Al4MAl4]q- (q=0-2; M=Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W), we used density functional theory (DFT) calculations (B3LYP/6-311+G(d) to design a series of novel non-transition-metal sandwich complexes based on the all-metal aromatic unit Al4(2-) and the main-group metals M (M=Li, Na, K, Be, Mg, Ca). The traditional homo-decked sandwich compounds [Al4MAl4]q- (without counterions) and (nM)q+[Al4MAl4]q- (with counterions M) (q=2-3, M=Li, Na, K, Be, Mg, Ca), although some of them are truly energy minima, have a much higher energy than many fused isomers. We thus concluded that it seems unlikely for Al4(2-) to sandwich the main-group metal atoms in the homo-decked sandwich form. Alternatively, we proposed a new type of sandwich complex, namely hetero-decked sandwich compounds [CpMAl4]q-, that are the ground-state structures for each M both with and without counterions. It was shown that with the rigid Cp- partner, the all-metal aromatic unit Al(4)2- might indeed act as a "superatom". These new types of all-metal aromatic unit-based sandwich complexes await future experimental verification.

Journal Article↗
PubMed2006

Theoretical mechanistic study on the radical-molecule reactions of cyanomethylidyne with PH3, H2S, and HCl.

The cyanomethylidyne (CCN) has been the long-standing subject of extensive theoretical and experimental studies on its structures and spectroscopies. However, there are few investigations on its reactivity. Our very recent theoretical work indicated that even with the simplest methane, the CCN reaction faces almost zero barriers following the carbyne mechanism as CH does. This was suggestive of the powerfulness of the nonatomic and nonhydrogenated CCN radical in depleting old molecules and synthesizing new cyanogen-containing molecules in either combustion or interstellar processes. In this paper, a detailed mechanistic study at the CCSD(T)/6-311+G(2df,p)//B3LYP/6-311g(d,p) and G2M(CC1)//B3LYP/6-311G(d,p) computational levels is reported for the reactions of CCN with a series of sigma-bonded molecules of the second row H(n)X (X,n) = (P,3), (S,2), and (Cl,1). The carbenoid insertion is confirmed as the most favored entrance channel, forming H(n) (-1)XC(H)CN. Subsequently, H(n) (-1)XC(H)CN will predominantly lead to product H(n) (-2)XC(H)CN+H via the H-extrusion processes (except X = Cl). Yet, the CCN+HX (X = Cl) reaction is the exception because XC(H)CN intrinsically has no H-atoms at X for extrusion or migration. At G2M(CC1)//B3LYP/6-311G(d,p) computational level, ClC(H)CN can only dissociate back to the reactant or be stabilized with its isomers upon sufficient collisions or radiation. The carbyne character confirmed in this paper provides a useful base for future experimental and theoretical study on the chemistry of this nonatomic and nonhydrogenated reactive radical. In addition, interestingly, the complexes H(n)X-CCN (X,n) = (P,3) and (S,2) formed in the reactions are found not to be the simple (loosely bound) donor-accepter complexes as those formed in the CCN insertions into other hydrides (NH(3), H(2)O, HF, HCl). On the basis of the comparison with the qualitative features of typical ylides, H(3)P--CCN and H(2)S--CCN are considered to be similar to the ylides in nature, being "ylide-like radicals." They might be observed in some experiments, since they are in deep potential wells on the energy surface.

Computer Simulation↗
PubMed2006

Theoretical study on the [Si, C, N, O] potential energy surface.

The structures, energetics, spectroscopies, and stabilities of the doublet [Si, C, N, O] radical are explored at the density functional theory and ab initio levels. Sixteen isomers are located, connected by 29 interconversion transition states. At the CCSD(T)/6-311+G(2df)//QCISD/6-311G(d)+ZPVE level, the lowest lying isomer is a linear SiNCO 1 (0.0 kcal/mol) mainly featuring a cumulene | . Si = N = C = O. The second and third low-lying isomers are bent OSiCN 2 (8.8) and bent OSiNC 3 (11.1), respectively. All the three low-lying isomers 1, 2, 3, and another high-lying species 5 (75.4) with a linear SiCNO structure are shown to have considerable kinetic stability and may be experimentally observable. The predicted results of isomers 1 and 2 are consistent with the previous mass spectrometry experiments. Moreover, the fourth low-lying species SiOCN 4 (23.9) with bent structure is expected to be observable in low-temperature environments. The bonding nature of the five isomers 1, 2, 3, 4, and 5 is analyzed. The calculated results are compared with those of the analogous molecules C(2)NO and Si(2)NO. Implications in interstellar space and N,O-doped SiC vaporization processes are also discussed.

Journal Article↗
PubMed2006

Ylidic radical-molecule reactions.

The known reactions between a neutral radical and a neutral closed-shell sigma-type molecule are generally associated with the atom/group-abstraction (e.g., CN, OH reactions) or the carbenoid insertion processes (e.g., CH reactions). In this article, we describe a new type of neutral radical-molecule reaction that feature the nucleophilic addition and elimination mechanism based on the systematic Gaussian-3//MP2(full)/6-31G(d) investigations on the PH(3)CH+HX model reactions (X = CH(3), NH(2), OH, F, CH(2)F, CHF(2), CF(3), NHCH(3)/CH(2)NH(2), OCH(3)/CH(2)OH). The novel properties are found to benefit both from the radical and ylidic characters of PH(3)CH, and the type of reagent HX determines the nucleophilic addition reactivity. The present work is the first study on the chemical reactivity of the ylidic radicals.

Computer Simulation↗
PubMed2006

Monosilicon-substituted cyanoacetylene: a computational study.

A detailed theoretical investigation of the [H,Si,C(2),N] potential energy surfaces including 28 minimum isomers and 65 interconversion transition states is reported at the Gaussian-3//B3LYP/6-31G(d) level. Generally, the triplet species lie energetically higher than the singlet ones. The former three low-lying isomers are linear HCCNSi 1 (0.00 kcal/mol), branched SiC(H)CN 12 (7.09 kcal/mol), and bent HNCCSi 7 (14.22 kcal/mol), which are separated by rather high barriers from each other and are kinetically very stable with the least conversion barriers of 32.6-70.5 kcal/mol. Two energetically high-lying isomers HCNCSi 3 (42.99 kcal/mol) and SiC(H)NC 13 (36.05 kcal/mol) are also kinetically stable with a barrier of 49.19 and 21.42 kcal/mol, respectively. Additionally, five high-lying isomers, that is, three chainlike isomers, HCCSiN 2 (55.17), HCSiNC 6 (47.80), HSiNCC 11 (78.83), and one three-membered ring isomer HN-cSiCC 19 (51.21), and one four-membered ring isomer cSiCN(H)C 27 (50.6 kcal/mol), are predicted to each have lower conversion barriers of 12-18 kcal/mol and can be considered as meta-stable species. All of the predicted 10 isomers could exist as stable or meta-stable intermediates under suitable conditions. Finally, the structural and bonding analysis indicate that the [H,Si,C(2),N] molecule contains various properties that are of chemical interest (e.g., silylene, SiC triple bonding, and conjugate SiN triple bonding and CC triple bonding, charge-transfer specie, planar aromatic specie, cumulate double bonding). This is the first detailed theoretical study on the potential energy surfaces of the series of hydrogenated Si,C,C,N-containing molecules. The knowledge of the present monohydrogenated SiC(2)N isomerism could provide useful information for more highly hydrogenated or larger Si,C(2),N-containing species.

Acetylene↗
PubMed2006

Radical reaction C3H+NO: a mechanistic study.

Although a number of hydrocarbon radicals including the heavier C(3)-radicals C(3)H(3) and C(3)H(5) have been experimentally shown to deplete NO effectively, no theoretical or experimental attempts have been made on the reactivity of the simplest C(3)-radical towards NO. In this article, we report our detailed mechanistic study on the C(3)H+NO reaction at the Gussian-3//B3LYP/6-31G(d) level by constructing the singlet and triplet electronic state [H,C(3),N,O] potential energy surfaces (PESs). The l-C(3)H+NO reaction is shown to barrierlessly form the entrance isomer HCCCNO followed by the direct O-elimination leading to HCCCN+(3)O on triplet PES, or by successive O-transfer, N-insertion, and CN bond-rupture to generate the product (1)HCCN+CO on singlet PES. The possible singlet-triplet intersystem crossings are also discussed. Thus, the novel reaction l-C(3)H+NO can proceed effectively even at low temperatures and is expected to play an important role in both combustion and interstellar processes. For the c-C(3)H+NO reaction, the initially formed H-cCCC-NO can most favorably isomerize to HCCCNO, and further evolution follows that of the l-C(3)H+NO reaction. Quantitatively, the c-C(3)H+NO reaction can take place barrierlessly on singlet PES, yet it faces a small barrier 2.7 kcal/mol on triplet PES. The results will enrich our understanding of the chemistry of the simplest C(3)-radical in both combustion and interstellar processes, which to date have received little attention despite their importance and available abundant studies on its structural and spectroscopic properties.

Computer Simulation↗
PubMed2006

Gaseous reaction mechanism of C2F radical with water.

The kinetic properties of the carbon-fluorine radicals are little understood except those of CFn (n =1-3). In this article, a detailed mechanistic study was reported on the gas-phase reaction between the simplest pi-bonded C2F radical and water as the first attempt to understand the chemical reactivity of the C2F radical. Various reaction channels are considered. The most kinetically competitive channel is the quasi-direct hydrogen-abstraction route forming P5 HCCF + OH. At the CCSD(T)/6-311+G(2d,2p)//B3LYP/6-311G(d,p)+ZPVE, CCSD(T)/6-311+G(3df,2p)//QCISD/6-311G(d,p)+ZPVE and Gaussian-3//B3LYP/6-31G(d) levels, the overall H-abstraction barriers (4.5, 4.7, and 4.2 kcal/mol) for the C2F + H2O reaction are comparable to the corresponding values (5.5, 3.7, and 5.7 kcal/mol) for the analogous C2H + H2O reaction. This suggests that C2F is a reactive radical like the extensively studied C2H, in contrast to the situation of the CF and CF2 radicals that have much lower reactivity than the corresponding hydrocarbon species. Thus, the C2F radical is expected to play an important role in the combustion processes of the carbon-fluorine chemistry. Furthermore, addition of a second H2O can catalyze the reaction with the H-abstraction barrier significantly reduced to a marginally zero value (0.5 kcal/mol). This is also indicative of the potential relevance of the title reactions in the low-temperature atmospheric chemistry.

Journal Article↗
PubMed2006

Theoretical study on structures and stabilities of [H,Ge,C,N].

Theoretical investigations are performed for the first time on the simplest hydrogenated germanium cyanide [H,Ge,C,N], whose analogs [H,C(2),N] and [H,Si,C,N] have been detected in space and laboratory, respectively. The detailed potential energy surfaces in both singlet and triplet states are constructed at the CCSD(T)/6-311+G(3df,2p)//B3LYP/6-31G(d)+ZPVE level, including 18 minimum isomers and 26 interconversion transition states. The former three low-lying and kinetically stabilized isomers are HGeCN (1)1 (0.0 kcal/mol), HGeNC (1)2 (5.1 kcal/mol), and cyclic cCHNGe(1)7 (11.1 kcal/mol). In addition, five isomers HCNGe (1)3 (33.8), HNCGe (1)5 (29.8), cNHCGe (1)8 (37.9), HGeCN (3)1 (30.1), and HNCGe (3)5 (26.5) each have considerable barriers, despite their high energies. Future laboratory characterization and astrophysical detection of the eight [H,Ge,C,N] isomers, especially the former three low-lying species (1)1, (1)2, and (1)7, are highly recommended. The accurate spectroscopic data at the QCISD/6-311G(d,p) level are provided. For some species, the CBS-QB3 calculations are also performed. Wherever possible, comparisons with the analogous [H,C(2),N] and [H,Si,C,N] are made on the structural, energetic, and bonding properties.

Chemical Phenomena↗
PubMed2006

Reaction mechanism of the CCN radical with nitric oxide.

To investigate the possibility of the carbyne radical CCN in removal of nitric oxide, a detailed computational study is performed at the Gaussian-3//B3LYP/6-31G(d) level on the CCN + NO reaction by constructing the singlet and triplet electronic state [C(2)N(2)O] potential energy surfaces (PESs). The barrierless formation of the chain-like isomers NCCNO (singlet at -106.5, triplet cis at -48.2 and triplet trans at -47.6 kcal/mol) is the most favorable entrance attack on both singlet and triplet PESs. Subsequently, the singlet NCCNO takes an O-transfer to form the branched intermediate singlet NCC(O)N (-85.6), which can lead to the fragments CN + NCO (-51.2) via the intermediate singlet NCOCN (-120.3). The simpler evolution of the triplet NCCNO is the direct N-O rupture to form the weakly bound complex triplet NCCN...O (-56.2) before the final fragmentation to NCCN + (3)O (-53.5). However, the lower lying products (3)NCN + CO (-105.6) and (3)CNN + CO (-74.6) are kinetically much less competitive. All the involved transition states for generation of CN + NCO and NCCN + (3)O lie much lower than the reactants. Thus, the novel reaction CCN + NO can proceed effectively even at low temperatures and is expected to play a role in both combustion and interstellar processes. Significant differences are found on the singlet PES between the CCN + NO and CH + NO reaction mechanisms.

Journal Article↗
PubMed2005

Mechanism of HCS + O2 reaction: hydrogen- or oxygen-transfer?

In spite of the potential importance of the HCS radical in both combustion and interstellar processes, its chemical reactivity has not been tackled previously. In the present paper, the oxidation reaction of the HCS radical is theoretically investigated for the first time at the CCSD(T)/6-311++G(3df,2p)//BH&HLYP/6-311++G(d,p)+ZPVE and Gaussian-3//B3LYP/6-31G(d) levels. It is shown that the most feasible pathway is the O2 addition to the HCS radical forming the intermediate SC(H)OO which can undergo a subsequent O-extrusion leading to SC(H)O + 3O. This features an indirect O-transfer mechanism with the overall barrier of 4.4 and 3.5 kcal mol(-1), respectively, at the two levels. However, formation of the H-transfer product CS + HO2 is kinetically much less feasible, i.e., the direct mechanism has barriers of 14.3 and 8.7 kcal mol(-1), whereas the indirect mechanism has barriers of 12.6 and 10.7 kcal mol(-1), respectively. This result is in sharp contrast to the analogous HCO + O2 reaction, where the direct (with a barrier of 2.98 kcal mol(-1)) and indirect (2.26 kcal mol(-1)) H-transfer processes are highly competitive over the indirect O-transfer process (the least endothermicity is 19.9 kcal mol(-1)). The possible explanations and implications of the present results are provided.

Algorithms↗
PubMed2005

Theoretical study on stability and properties of NC2O isomers.

The structures, energetics, spectroscopies, and stabilities of the doublet NC(2)O radical are explored at density functional theory and ab initio levels. Nine minimum isomers are located connected by 22 interconversion transition states. At the CCSD(T)/6-311+G(2df)//QCISD/6-311G(d)+ZPVE level, the lowest-lying isomer is bent NCCO 1 (0.0 kcal/mol) with (2)A' state followed by bent isomer CNCO 2 (16.7). Two isomers (1 and 2) and another high-lying species CCNO 4 (99.4) with bent structure are considerably stabilized by a barrier of at least 20 kcal/mol. All of the three isomers should be experimentally or astrophysically observable. This result is consistent with their indication of neutralization-reionization mass spectrometry experiments. Also, the calculated spectroscopic properties and bond distances of known NCCO 1 are consistent with recent experimental observations and theoretical studies. The bonding natures of the isomers 1, 2, and 4 are analyzed. Their molecular properties including the heats of formation, adiabatic ionization potentials, and adiabatic electronic affinities are calculated at the higher levels G3//B3LYP, G3(MP2)//B3LYP, QCISD, and CCSD(T) (single-point). Possible formation strategies of the isomers 1, 2, and 4 in laboratory and space are also discussed in detail.

Journal Article↗
PubMed2005

Theoretical study on structures and stability of C4P isomers.

The structures, energetics, spectroscopies, and stabilities of doublet C(4)P isomeric species are explored at the DFT/B3LYP, QCISD, and CCSD(T) (singlet-point) levels. A total of 12 minimum isomers and 27 interconversion transition states are located. At the CCSD(T)/6-311G(2df)//QCISD/6-311G(d)+ZPVE level, the lowest-lying isomer is a floppy CCCCP 1 (0.0 kcal/mol) mainly featuring a cumulenic structure |C=C=C=C=P*|, which differs much from the analogous C4N radical (|*C-C[triple bond]C-C[triple bond]N|). The quasi-linearity and the low bending mode of 1 are in contrast to the previous prediction. The second energetically followed isomer PC-cCCC 3 (14.9 kcal/mol) possesses a CCC ring-bonded to CP. The two low-lying isomers are separated by a high-energy ring-closure/open transition state (26.5 kcal/mol) and thus are very promising candidates for future laboratory and astrophysical detection. Furthermore, four high-energy isomers, that is, two bent isomers CCPCC 2 (68.4 kcal/mol) and CCPCC 2' (68.5 kcal/mol) and two cagelike species 10 (56.0 kcal/mol) and 11 (67.9 kcal/mol), are also stabilized by considerable barriers. The present work is the first detailed potential energy survey of CnP clusters and can provide useful information for the investigation of larger CnP radicals and for understanding the isomerism of P-doped C vaporization processes.

Journal Article↗
PubMed2005

Radical-molecule reaction C3H+H2O: a mechanistic study.

Despite the importance of the C(3)H radical in both combustion and interstellar space, the reactions of C(3)H toward stable molecules have never been studied. In this paper, we report our detailed mechanistic study on the radical-molecule reaction C(3)H+H(2)O at the Becke's three parameter Lee-Yang-Parr-B3LYP6-311G(d,p) and coupled cluster with single, double, and triple excitations-CCSD(T)6-311G(2d,p) (single-point) levels. It is shown that the C(3)H+H(2)O reaction initially favors formation of the carbene-insertion intermediates HCCCHOH (1a,1b) rather than the direct H- or OH-abstraction process. Subsequently, the isomers (1a,1b) can undergo a direct H- extrusion to form the well-known product propynal HCCCHO (P(5)). Highly competitively, (1a,1b) can take the successive 1,4- and 1,2-H-shift interconversion to isomer H(2)CCCHO(2a,2b) and then to isomer H(2)CCHCO(3a,3b), which can finally take a direct C-C bond cleavage to give product C(2)H(3) and CO (P(1)). The other products are kinetically much less feasible. With the overall entrance barrier 10.6 kcal/mol, the title reaction can be important in postburning processes. Particularly, our calculations suggest that the title reaction may play a role in the formation of the intriguing interstellar molecule, propynal HCCCHO. The calculated results will also be useful for the analogous C(3)H reactions such as with ammonia and alkanes.

Journal Article↗
PubMed2004

Si2CN: a stable nitrogen-containing radical with cyclic ground state.

The structures and isomerization of Si(2)CN species are explored at density functional theory and ab initio levels. Fourteen minimum isomers are located connected by 23 interconversion transition states. At the coupled-cluster single double (CCSD)(T)/6-311+G(2df)//QCISD/6-311G(d) +zero-point vibrational energies level, the thermodynamically most stable isomer is a four-membered ring form cSiSiCN 1 with Si-C cross bonding. Isomer 1 has very strong C-N multiple bonding characters, formally suggestive of a radical adduct between Si(2) and CN. Such a highly pi-electron localization can effectively stabilize isomer 1 to be the ground state. The second low-lying isomer is a linear form SiCNSi 5 (9.8 kcal/mol above 1) with resonating structure among [Si=C-*N=Si], *[Si=C=N=Si], and [Si=C=N-Si*]* with the former two bearing more weight. The species 1 and 5 have very high kinetic stability stabilized by the barriers of at least 25 kcal/mol. Both isomers should be experimentally or astrophysically observable. In light of the fact that no cyclic nitrogen-containing species have been detected in space, the cyclic species 1 could be a very promising candidate. The calculated results are compared to those of the analogous molecules C(3)N, C(3)P, SiC(2)N, and SiC(2)P. Implications of Si(2)CN in interstellar and N-doped SiC vaporization processes are also discussed.

Journal Article↗
PubMed2002

Direct ab initio dynamics study on the rate constants and kinetic isotope effect for the reactions of H atoms with GeDn(CH3)4-n (n = 1-4).

Direct ab initio dynamic calculations are performed on the reactions of atomic hydrogen with GeD(n)(CH(3))(4-n) (n = 1-4) over the temperature range 200-2000 K at the PMP4SDTQ/6-311 +G(3df,2p)//MP2/6-31 +G(d) (for n = 2-4) and G2//MP2/6-31 +G(d) (for n = 1) levels. The corresponding k(H)/k(D) ratios are then calculated in order to determine the kinetic isotope effect for the four reactions. For the simplest GeD(4) +H reaction, the only one that has available experimental data, the calculated canonical variational transition state theory incorporates small-curvature tunneling correction (CVT/SCT) thermal rate constants, and the k(H)/k(D) values are in good agreement with the experimental values within the experimental temperature range 293-550 K. For the four GeD(n)(CH(3))(4-4) (n = 1-4) reactions, the variational effect is small over the whole temperature range, whereas the small-curvature effect is important in the lower temperature range. Finally, the overall rate constants are fitted to the three-parameter expression over the whole temperature range 200-2000 K as 5.8 x 10(8)T(1.68)exp(-929/T), 1.7 x 10(8)T(1.80)exp(-691/T), 2.58 x 10(8)T(1.71)exp(-706/T), and 1.0 x 10(7)T(2.08)exp(-544/T) cm(3) mol(-1) s(-1) for the n = 4, 3, 2, and 1 reactions. Our work may represent the first theoretical study of the kinetic isotope effect for the H-attack on the G-H bonding.

Journal Article↗
PubMed2002

Theoretical study on the mechanism of the 1CHCl + NO reaction.

The complex doublet potential energy surface of the CHClNO system, including 31 minimum isomers and 84 transition states, is investigated at the QCISD(T)/6-311G(d, p)//B3LYP/6-31G(d, p) level in order to explore the possible reaction mechanism of the singlet CHCl with NO. Various possible isomerization and dissociation channels are probed. The initial association between 1CHCl and NO at the terminal N-site can almost barrierlessly lead to the chainlike adducts HClCNO a (a1, a2) followed by the direct Cl-extrusion to product P9 Cl + HCNO, which is the most feasible channel. Much less competitively, a (a1, a2) undergoes a ring-closure leading to the cyclic isomer c-C(HCl)NO d followed by a concerted Cl-shift and N-O cleavage of d to form the branched isomers ClNC(H)O f (f1, f2). Eventually, f (f1, f2) may take a direct H-extrusion to produce P7 H + ClNCO or a concerted 1,2-H-shift and Cl-extrusion to form P1 Cl + HNCO. The low-lying products P2 HCl + NCO, P3 Cl + HOCN, P14 HCO + 3NCl, P6 ClO + HCN, and P13 ClNC + OH may have the lowest yields observed. Our calculations show that the product distributions of the title reaction are quite different from those of the analogous 1CHF + NO reaction, yet are similar to those of another analogous 3CH2 + NO reaction. The similarities and discrepancies among the three reactions are discussed in terms of the substitution effect. The present article may assist in future experimental identification of the product distributions for the title reaction and may be helpful for understanding the halogenated carbene chemistry.

Journal Article↗