and Au(I) Complexes with Planar Tetracoordinate Carbon Using Novel

Aug 22, 2012 - horizontal C−C bond obey the octal rule. The WBIs of the chemical bonds in AuCl(L) (L = CO, NHC, CNCH3,. CH2P(CH3)3, A, and F−J) ar...
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Toward Design of Ag(I) and Au(I) Complexes with Planar Tetracoordinate Carbon Using Novel Ligands Congjie Zhang* and Feifei Li Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China S Supporting Information *

ABSTRACT: We have designed a family of novel molecules that can act as a donor at a carbon atom to coordinate with Ag(I) and Au(I) to achieve stable complexes with a planar tetracoordinate carbon (ptC). Then, a kind of new strategy for the design of the compound with a ptC was provided.

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orbitals (HOMOs) of these molecules are σ donor type orbitals at the carbon atom and similar to that of CO, carbene, CNCH3, and CH2PR3. Furthermore, we have investigated a series of Ag(I) and Au(I) complexes coordinated with these novel molecules. The reason for choosing Ag(I) and Au(I) is that the complexes of MCl(CO), MCl(NHC), M(NHC)2+ (M = Ag(I) and Au(I), NHC is a N-heterocyclic carbene), and the Au(I) complexes coordinated with CH2PR3 prepared experimentally20,24−29 as well as the complexes formed by these novel molecules with AgCl and AuCl have small steric effects. Fortunately, the lowest energy structures of these complexes are stable and have a tetragonal planar carbon, indicating that these complexes contain a planar tetracoordinate carbon (ptC). As we know, Hoffmann has ever proposed a carbon atom that can form compounds with ptC in 1970.30 Unfortunately, only a few of clusters (CAl3Si−, CAl3Ge−, and CAl4Na−)31,32 and complexes (V2(C8H9O2)4 ·2C4H8O, Cl3WC3H3, and its derivatives)33−36 were achieved experimentally to date. Thus, we anticipate that a kind of new strategy for the design of the compound with ptC was provided by studying the structures and properties of these complexes.

INTRODUCTION CO is a very general ligand that coordinates with transition metal by σ donor via the lone pair at the carbon atom to form transition metal carbonyl complex. Moreover, transition metal carbonyl complexes play a very important role in organometallic chemistry and coordination chemistry.1 Besides CO, another three kinds of molecules, carbene, CNR, and CH2PR3 (R = H, alkyl groups, or phenyl groups) also can coordinate with the transition metal by σ donor at the carbon atom to obtain stable complexes. Carbene can be traced back to Dumas’s work.2 However, since the first Fischer and Schrock carbenes were synthesized in 1964 and 1974, respectively,3,4 up to now, plenty of carbene complexes have been obtained and applied to many reactions, which have been reviewed.5−13 The complexes formed by CNR with transition metal (Cr, Mo, W, Fe(II), Ru(II), and so on) have also been synthesized.14−19 In addition, experimentally, CH2PR3 coordinates with transition metal to obtain some complexes,20−23 such as, Au(CH2P(S)Ph2)2, Au2Pt(CH2P(CH2P(S)Ph2))4, and Au2Pt(CH2P(S)Ph2)4Cl2.20 Now, we look at chemical bonds relating to the carbon of the carbonyl complexes and carbene complexes, as well as the CNCH3 and CH2PR3 complexes in detail. We found that the carbonyl complex and CNCH3 complex have a linear carbon, the carbene complex has a trigonal planar carbon, and the CH2PR3 complex contains a tetrahedron carbon. There is currently no other molecules coordinated with transition metal by σ donor at the carbon atom to obtain a transition metal complex besides CO, carbenes, CNCH3, and CH2PR3. Here, we obtained a family of novel stable molecules C3H2BX (X = CH3, CH2C(CH3)3, CH2C(CN)3, Cl, NO2, and OH) with two three-membered rings, and the highest occupied molecular © 2012 American Chemical Society

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COMPUTATIONAL METHODS The geometries of the molecules studied here were optimized using density functional theory calculations at the B3LYP level. Frequency at the same level of theory were also calculated to confirm all minima. In addition, we used the MP2/6-311+ +G** method to perform the calculations of the structures and Received: June 14, 2012 Revised: August 16, 2012 Published: August 22, 2012 9123

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Figure 1. Optimized geometries of CO, NHC, CNCH3, and CH2P(CH3)3 and the lowest energy structures of C3H2BX (X = CH3, CH2CH3, CH(CH3)2, C(CH3)3, CF3, CH2C(CH3)3, CH2C(CN)3, Cl, NO2, OH, and NH2) at the B3LYP/6-311++G** level.

Figure 2. HOMOs of CO, NHC, CNCH3, CH2P(CH3)3, and the lowest energy structures of C3H2BX (X = CH3, CH2CH3, CH(CH3)2, C(CH3)3, CF3, CH2C(CH3)3, CH2C(CN)3, Cl, NO2, OH, and NH2).

vibrational frequencies of C3H2BX (X = CH3 and CH2(CH3)) in order to check the B3LYP method. The effective core potentials (ECP) of Hay and Wadt with the double-ζ valence basis sets (LanL2DZ)37,38 were used to describe Ag(I) and Au(I), while the 6-311++G** basis sets were employed for other atoms. Wiberg bond indices (WBIs) of the most stable Ag(I) and Au(I) complexes were obtained by natural bond orbital (NBO) analysis.39 The electronic spectra of the Ag(I) and Au(I) complexes were achieved by the time-dependent density functional response theory (TD-B3LYP). 40 All calculations were performed with the Gaussian03 program.41

Scheme 1. Structures of Complexes Formed by MCl and A−J (M = Ag(I) or Au(I); Y = C or B)

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of the position of the boron atom and the conformation of X with respect to the C3H2B part, each molecule has some isomers. Optimized geometries and relative energies of the 11 molecules together with their isomers were displayed in Figure 1S (in Supporting Information). As seen from Figure 1S, for convenience, the lowest energy structures of C3H2BX (X = CH3, CH2CH3, CH(CH3)2, C(CH3)3, CF3, CH2C(CH3)3,

RESULTS AND DISCUSSION We have designed 11 kinds of molecules C3H2BX (X = CH3, CH2CH3, CH(CH3)2, C(CH3)3, CF3, CH2C(CH3)3, CH2C(CN)3, Cl, NO2, OH, and NH2) with two three-membered rings in which these groups (X) were chosen according to the steric effect and conjugate effect. For the 11 molecules, because 9124

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Figure 3. Optimized geometries and relative energies (in kcal/mol) of AgClL with ptC (L = CO, NHC, CNCH3, CH2P(CH3)3, C3H2BCH3, C3H2BCH2C(CH3)3, C3H2BCH2C(CN)3, C3H2BCl, C3H2BNO2, and C3H2BOH).

Figure 4. Optimized geometries and relative energies (in kcal/mol) of AuClL with ptC (L = CO, NHC, CNCH3, CH2P(CH3)3, C3H2BCH3, C3H2BCH2C(CH3)3, C3H2BCH2C(CN)3, C3H2BCl, C3H2BNO2, and C3H2BOH).

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Figure 5. Optimized geometries and relative energies (in kcal/mol) of MClL (M = Ag(I) and Au(I); L = C2BH2CCH2CH3, C2BH2CCH(CH3)2, C2BH2CC(CH3)3, and C2BH2CCF3).

lengths of two C−N bonds and C−C bond of C3N2H4 are 1.366, 1.393, and 1.354 Å, respectively, which are consistent with those of the derivatives of C3N2H4, 1,3-di-1-adamantylimidazol-2-ylidene.42 The C−C and C−B in the two threemembered rings of A and F−K are between 1.455 and 1.478, and 1.435 and 1.463 Å, respectively. The bond distances of the horizontal B−C bond in B−E are longer than that of A and F− K by about 0.2 Å. In order to gain insight into the coordination properties of A−K, we depicted the HOMOs of A−K, as well as CO, NHC, CNCH3, and CH2PR3 in Figure 2. As illustrated in Figure 2, the main parts of the HOMO of CO, NHC, CNCH3, and CH2PR3 situate at their carbon atoms. The main parts of HOMOs of A, F to J distribute two sides of the horizontal C−C bond. The main parts of HOMOs of B−E locate on two edges of the horizontal B−C bond in which the component of the B atom is greater than that of the C atom. The HOMO of K is a π orbital. The order of the energies of the HOMOs of CO, NHC, CNCH3, CH2P(CH3)3, and A−J are CO < CNCH3 ≈ I < G < H < J < F < A < E < B ≈ C ≈ D < NHC < CH2P(CH3)3. Thus,

CH2C(CN)3, Cl, NO2, OH, and NH2) are denoted with symbols of A, B, C, D, E, F, G, H, I, J, and K, respectively. In addition, we found the lowest structures of C3H2BX (X = CH3 and CH2(CH3)) obtained at the B3LYP/6-311++G** level are in good agreement with those at the MP2 level. Then, we collected the optimized geometries of A to K, together with CO, C3N2H4 (a kind of simple NHC), CNCH3, and CH2PR3 in Figure 1. Calculated vibrational frequencies of the fifteen molecules indicate that they situate at the minima of the potential energy surfaces. Moreover, the eleven molecules (A− K) can be classified into two types, one type is the boron atom of the C3H2B part bonds to X, which are A, F, G, H, I, J, and K; and another type is the carbon atom of the C3H2B part bonds to X, which are B, C, D, and E. Obviously, the lowest energy structures of C3H2BX depend upon the X. Moreover, the structures of A−G indicate that the hydrogen of the −CH3 group of C3H2BCH3 is replaced with −CH3, −C(CH3)3, −C(CN)3, and −F, to result in different lowest energy structures. As seen from Figure 1, the bond length of C−O of CO is 1.128 Å, close to the experimental value. The bond 9126

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Figure 6. Selected Wiberg Bond Indices of the most stable structures AuClL (L = CO, NHC, CNCH3, CH2P(CH3)3, C3H2BCH3, C3H2BCH2C(CH3)3, C3H2BCH2C(CN)3, C3H2BCl, C3H2BNO2, and C3H2BOH).

A to J can coordinate with transition metals by a σ donor via the attack of C or B, as shown in Scheme 1. So, we constructed the complexes of AgCl and AuCl coordinated with CO, NHC, CNCH3, CH2P(CH3)3, and A−J ligands. Optimized geometries and relative energies of AgCl(L) and AuCl(L) (L = A and F−J) were displayed in Figures 3 and 4 respectively, and those of MCl(L) (M = Ag(I) and Au(I); L = B, C, D, and E) were shown in Figure 5. As illustrated in Figures 3−5, MCl(L) (M = Ag(I) and Au(I); L = A−G and J) have two kinds of isomers due to the asymmetry of HOMOs of the ligands L, while MCl(L) (M = Ag(I) and Au(I); L = CO, NHC, CNCH3, CH2P(CH3)3, I, and J) have single structure. Figures 3−5 also show that the lower energy structures of AgCl(L) and AuCl(L) (L = A and F−J) are that the big groups or electron pair are away from Ag(I) or Au(g) due to the steric effect. Calculated vibrational frequencies of the lower structures in Figures 3−5 are positive, indicating they are the minima on the potential energy surfaces. According to the chemical bonds relating to the C(M) atom of MCl(L) (M = Ag(I) and Au(I); L = CO, NHC, CNCH3,

CH2P(CH3)3, A, and F−J), the C(M) atom was classified into four types, which are line, trigonal planar, tetrahedron, and planar tetracoordinate carbon, in which the novel ligands A and F−J act as σ donor to yield complexes MCl(L) (M = Ag(I) and Au(I); L = A and F−J) containing a ptC. As for AgCl(L) and AuCl(L) (L = B−E), the lower energy structure of AgCl(L) and AuCl(L) attacks the boron atom of the ligands L but not the carbon atom. So ligands B−E can not form complexes containing ptC with AgCl or AuCl. As can be seen from Figures 3 and 4, the bond distances of Cl−Ag and C−Ag of AgCl(CO) are 2.339 and 2.097, same as those of previous theoretical results.25 The optimized bond distances of Ag−C and Au−C of AgCl(NHC) and AuCl(NHC) are 2.124 and 1.994 Å, respectively, consistent with the experimental values 2.116(8) (Ag−C) and 1.983(3)Å (Au−C) of {[1-(benzyl)-3-(N-tert-butylacetamido)imidazol-2-ylidene]MCl}2 [M = Ag(I) and Au(I)],26 and the bond lengths of Ag−Cl and Au−Cl of AgCl(NHC) and AuCl(NHC) are also in good agreement with that of experiment.26 The bond lengths of M−C and M−Cl of MCl(NHC) (M = Ag(I) and Au(I)) are 9127

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Table 1. Symmetry (symm.), Energy of HOMO (EHOMO) and LUMO (ELUMO), Energy Gaps (Egap, in eV), Electronic Configuration (EC) of Ag(I) and Au(I), Binding Energies (Eb, in kcal/mol), and Free Energies (G, in kcal/mol) with Respect to (L + MCl) of the Most Stable Structures MClL (M = Ag(I) and Au(I); L = CO, NHC, CNCH3, CH2P(CH3)3, C3H2BCH3, C3H2BCH2C(CH3)3, C3H2BCH2C(CN)3, C3H2BCl, C3H2BNO2, and C3H2BOH) complexes

symm.

EHOMO

ELUMO

Egap

EC

Eb

G

AgClCO AgClNHC AgClCNCH3 AgClCH2P(CH3)3 AgCl C3H2BCH3 AgClC3H2BCH2C(CH3)3 AgClC3H2BCH2C(CN)3 AgClC3H2BCl AgClC3H2BNO2 AgClC3H2BOH AuClCO AuClNHC AuClCNCH3 AuClCH2P(CH3)3 AuClC3H2BCH3 AuClC3H2BCH2C(CH3)3 AuClC3H2BCH2C(CN)3 AuClC3H2BCl AuClC3H2BNO2 AuClC3H2BOH

C∞v C2v C3v Cs Cs Cs Cs Cs Cs Cs C∞v C2v C3v Cs Cs Cs Cs Cs Cs Cs

−0.266 −0.226 −0.239 −0.218 −0.242 −0.241 −0.257 −0.246 −0.248 −0.256 −0.291 −0.235 −0.257 −0.220 −0.253 −0.252 −0.270 −0.259 −0.271 −0.261

−0.116 −0.041 −0.060 −0.045 −0.101 −0.098 −0.126 −0.114 −0.103 −0.146 −0.106 −0.041 −0.055 −0.045 −0.098 −0.095 −0.122 −0.110 −0.143 −0.100

4.08 5.03 4.87 4.71 3.84 3.89 3.56 3.59 3.95 2.99 5.03 5.28 5.50 4.76 4.22 4.27 4.03 4.05 3.48 4.38

5s0.504d9.81 5s0.574d9.83 5s0.514d9.82 5s0.554d9.86 5s0.464d9.85 5s0.464d9.85 5s0.464d9.84 5s0.464d9.85 5s0.444d9.84 5s0.474d9.85 6s0.865d9.57 6s0.915d9.65 6s0.865d9.60 6s0.885d9.72 6s0.805d9.64 6s0.805d9.64 6s0.805d9.64 6s0.795d9.64 6s0.785d9.63 6s0.825d9.64

17.76 44.55 31.33 45.81 25.67 26.37 21.41 22.08 17.87 25.08 40.71 68.96 53.96 66.33 43.78 44.49 39.70 39.68 35.55 43.66

8.77 34.58 21.82 35.88 16.40 16.94 12.29 13.31 8.89 15.85 30.93 58.36 43.84 55.87 33.25 34.12 29.16 29.96 25.56 33.48

consistent with theoretical values at the MP2 level. 43 Furthermore, we found that the bond lengths of C−Ag and C−Au are about 2.07 and 2.0 Å of the complexes of AgCl and AuCl coordinated with other carbenes, respectively.44−46 Obviously, the calculated bond lengths of C−Ag and C−Au are consistent with the experimental values. The bond distances of C−Ag and C−Au of MCl(CNCH3) (M = Ag(I) and Au(I)) are closed to that of MCl(CO) (M = Ag(I) and Au(I)), which are 2.093 and 1.939 Å, respectively. The bond length of C−Ag of AgCl(CH2P(CH3)3) is greater than that of AgCl(NHC) by 0.063 Å. Similarly, the bond distance of C−Au of AuCl(CH2P(CH3)3) is longer than that of AuCl(NHC). Thus, the C−Ag and C−Au bonds of AgCl(CH2P(CH3)3) and AuCl(CH2P(CH3)3) are single bonds. The bond length of C−Au of AuCl(CH2P(CH3)3) is 2.091 Å, which agrees well with that of the complexes Au(CH2P(S)Ph2)2, Au2Pt(CH2P(CH2P(S)Ph2))4, and Au2Pt(CH2P(S)Ph2)4Cl2.20 The Ag−C and Ag− Cl of AgCl(L) (L = A and F−J) are about 2.16 and 2.36 Å ,respectively, and the Au−C and Au−Cl of AuCl(L) (L = A and F to J) are about 2.00 and 2.32 Å, respectively. Calculated bond distances of Ag−C and Au−C of MCl(L) (M = Ag(I) and Au(I); L = A and F to J) are between those of MCl(NHC) (M = Ag(I) and Au(I)) and MCl(CH2P(CH3)3) (M = Ag(I) and Au(I)). The bond lengths of Ag−Cl and Au−Cl have little difference in the most stable complexes of MCl(L) (M = Ag(I) and Au(I); L = CO, NHC, CNCH3, CH2P(CH3)3, A, and F− J). The bond distances of (Ag)C−C (horizontal direction), (Ag)C−C, and (Ag)C−B are 1.454−1.473, 1.514−1.537, and 1.479−1.526 Å, respectively. The bond distances of (Au)C−C (horizontal direction), (Au)C−C, and (Au)C−B are 1.456− 1.483, 1.521−1.572, and 1.509−1.571 Å, respectively. Therefore, the bond distances relating to C(M) show that C(M) is a ptC. For the sake of further confirming the chemical bonds, we have calculated the WBIs of the lower energy structures of AgCl(L) and AuCl(L) (L = CO, NHC, CNCH3, CH2P(CH3)3,

A, and F−J) in Figures 3 and 4, and the results are given in Figure 6. Figure 6 indicates that the WBIs of C−Ag in AgCl(L) (L = CO, NHC, CNCH3, and CH2P(CH3)3) are around 0.40, while the WBIs of C−Ag in AgCl(L) (L = A and F−J) are close to 0.25; thus, the Ag−C bond is slightly weaker than that of AgCl(CO) and AgCl(NHC). The WBIs of two C−C (horizontal direction), (Ag)C−C, and (Ag)C−B bonds are about 1.3, 1.0, and 1.0, respectively, the carbon atom bond to Ag(I) is further confirmed to be of a ptC. The total WBI of the ptC is about 3.57; the WBIs of C−C and C−B with respect to another horizontal carbon atoms are greater than 1.0, and the total WBIs are 3.73. Therefore, the two carbon atoms of the horizontal C−C bond obey the octal rule. The WBIs of the chemical bonds in AuCl(L) (L = CO, NHC, CNCH3, CH2P(CH3)3, A, and F−J) are very similar to those of AgCl(L). The dominant difference between AuCl(L) and AgCl(L) is that the WBIs of C−Au in AuCl(L) (L = CO, NHC, CNCH3, CH2P(CH3)3, A, and F−J) are greater than that of the corresponding C−Ag. The WBIs of Au−C in AuCl(L) (L = A and F−J) are close to 0.50. In addition, the carbon atom bonded to Au(I) is also a ptC. The calculated electronic configuration of Ag(I) and Au(I) of AgCl(L) and AuCl(L) (L = CO, NHC, CNCH3, CH2P(CH3)3, A, and F−J) are listed in Table 1. Table 1 indicates that electronic configurations of Ag(I) and Au(I) in different complexes have no significant difference, which the electronic configuration of Ag(I) and Au(I) are about 5s0.544d9.8 and 6s0.855d9.60, respectively. Together with the variation of the bond length of C−O of AgCl(CO) and AuCl(CO), AuCl(CO) has π-back effect, but AgCl(CO) does not. Calculated electronic spectra of AgCl(L) and AuCl(L) (L = CO, NHC, CNCH3, CH2P(CH3)3, A, and F−J) were depicted in Figure 7. Figure 7 indicates that the first electronic transition energy of AgCl(L) (L = CO, NHC, CNCH3, and CH2P(CH3)3) situate at 335, 279, 280, and 293 nm, respectively. The electronic transition energies of AgCl(L) (L = A and F−J) are 9128

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for Au(I) complexes, the binding energy of AuCl(NHC) is the largest, and the binding energy of AgCl(CH2P(CH3)3) is second to that of AuCl(NHC). The binding energy of other complexes is close to 40 kcal/mol. The free energies for MCl + L → MCl(L) (M = Ag(I) and Au(I)) are greater than 8.7 and 25.5 kcal/mol, respectively. So, CO, NHC, CNCH3, CH2P(CH3)3, A, and F−J can coordinate with AgCl and AuCl to obtain stable complexes.

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SUMMARY In summary, we have designed a family of novel molecules whose HOMOs are similar to those of CO, carbene, CNCH3, and CH2P(CH3)3. These molecules can coordinate with Ag(I) and Au(I) via σ donor at the carbon atom of these molecules to yield stable complexes with a ptC atom. That is, a kind of new strategy for the design of the compound with ptC was presented. Thus, we have extended the bonding model of the carbon atom as a σ donor compared to the structures and chemical bonds of MCl(L) (M = Ag(I) and Au(I); L = CO, NHC, CNCH3, and CH2P(CH3)3). These new molecules and complexes might be applied to organic chemistry and organmetallics if they are synthesized.

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ASSOCIATED CONTENT

S Supporting Information *

Optimized geometries and relative energies of C3H2BX (X = CH3, CH2CH3, CH(CH3)2, C(CH3)3, CF3, CH2C(CH3)3, CH2C(CN)3, Cl, NO2, OH, and NH2) at B3LYP/6-311++G** and MP2/6-311++G** levels. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the Fundamental Research Funds for the Central Universities (GK201002013) and State Key Laboratory for Physical Chemistry of Solid Surface (Xiamen University) (2010).

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Figure 7. Electron spectra of AgClL (a) and AuClL (b) (L = CO, NHC, CNCH3, CH2P(CH3)3, C3H2BCH3, C3H2BCH2C(CH3)3, C3H2BCH2C(CN)3, C3H2BCl, C3H2BNO2, and C3H2BOH).

REFERENCES

(1) Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th ed.; Wiley: New York, 1999. (2) Dumas, J. B. Ann. Chim. Phys. 1835, 58, 28. (3) Fischer, E. O.; Maasböl, A. Angew. Chem., Int. Ed. 1964, 3, 580. (4) Schrock, R. R. J. Am. Chem. Soc. 1974, 96, 6796. (5) Bourissou, D.; Guerret, O.; Gabbaï, F. P.; Bertrand, G. Chem. Rev. 2000, 100, 39. (6) Brahms, D. L. S.; Dailey, W. P. Chem. Rev. 1996, 96, 1585. (7) Enders, D.; Niemeier, O.; Henseler, A. Chem. Rev. 2007, 107, 5606. (8) Vignolle, J.; Cattoën, X.; Bourissou, D. Chem. Rev. 2009, 109, 3333. (9) Hirai, K.; Iton, T.; Tomioka, H. Chem. Rev. 2009, 109, 3275. (10) Arduengo, A. J.; Bertrand, G. Chem. Rev. 2009, 109, 3209. (11) Schuster, O.; Yang, L.; Raubenheimer, H. G.; Albrecht, M. Chem. Rev. 2009, 109, 3445. (12) Asay, M.; Jones, C.; Driess, M. Chem. Rev. 2011, 111, 354. (13) Benhamou, L.; Chardon, E.; Lavigne, G.; Bellemin-Laponnaz, S.; César, V. Chem. Rev. 2011, 111, 2705. (14) Fehlhammer, W. P.; Fritz, M. Chem. Rev. 1993, 93, 1243.

372, 367, 405, 400, 450, and 362 nm, respectively. The first electronic transition energies of AuCl(L) (L = CO, NHC, CNCH3, and CH2P(CH3)3) are 256, 264, 239, and 290 nm, respectively. The electronic transition energy of AuCl(L) (L = A and F−J) is 324, 322, 341, 338, 361, and 316 nm, respectively, greater than that of corresponding AgCl(L) complexes and lower than that of AgCl(CO) and AuCl(NHC). Thermochemistry was calculated for MCl + L → MCl(L) (M = Ag(I) and Au(I); L = CO, NHC, CNCH3, CH2P(CH3)3, A, and F−J). The calculated relative electronic energies and free energies were listed in Table 1. As seen from Table 1, the binding energy of AgCl(CO) is 17.76 kcal/mol, which is consistent with the calculated value in a previous paper.25 The binding energy of AgCl(CH2P(CH3)3) and AgCl(CO) is the maximum and minimum, respectively, and that of the AgCl(L) (L = A and F−J) ranges between 17.76 and 45.81 kcal/mol. As 9129

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(15) Mayr, A.; Guo, J. Inorg. Chem. 1999, 38, 921. (16) Seino, H.; Nonokawa, D.; Nakamura, G.; Mizobe, Y.; Hidai, M. Organometallics 2000, 19, 2002. (17) Zhang, X.; Emge, T. J.; Ghosh, R.; Goldman, A. S. J. Am. Chem. Soc. 2005, 127, 8250. (18) Hashimoto, H.; Sato, J.; Tobita, H. Organometallics 2009, 28, 3963. (19) Cheung, A. W.; Lo, L. T.; Ko, C.; Yiu, S. Inorg. Chem. 2011, 50, 4798. (20) Murray, H. H.; Briggs, D. A.; Garzon, G.; Raptis, R. G.; Porter, L. C.; Fackler, J. P. Organometallics 1987, 6, 1992. (21) Wang, S.; Fackler, J. P., Jr.; Carlson, T. F. Organometallics 1990, 9, 1973. (22) Fackler, J. P.; Kresinski, R. A. Organometallics 1991, 10, 3392. (23) Carlson, F. T.; Fackler, J. P., Jr.; Staples, R. J.; Winpenny, R. E. P. Inorg. Chem. 1995, 34, 426. (24) Mancho, W.; Gail, H. Chem. Ber. 1925, 58, 2175. (25) Shao, L.; Zhang, L.; Zhou, M.; Qin, Q. Organometallics 2001, 20, 1137. (26) Ray, L.; Shaikh, M. M.; Ghosh, P. Inorg. Chem. 2008, 47, 230. (27) Hintermair, U.; Englert, U.; Leitner, W. Organometallics 2011, 30, 3726. (28) Hashmi, A. S. K.; Yu, Y.; Rominger, F. Organometallics 2012, 31, 895. (29) Cure, J.; Poteau, R.; Gerber, I. C.; Gornitzka, H.; Hemmert, C. Organometallics 2012, 31, 619. (30) Hoffmann, R.; Alder, R. W.; Wilcox, C. F., Jr. J. Am. Chem. Soc. 1970, 92, 4992. (31) Wang, L. S.; Boldyrev, A. I.; Li, X.; Simons, J. J. Am. Chem. Soc. 2000, 122, 7681. (32) Boldyrev, A. I.; Wang, L. S. J. Phys. Chem. A 2001, 105, 10759. (33) Cotton, F. A.; Millar, M. J. Am. Chem. Soc. 1977, 99, 7886. (34) Pedersen, S. F.; Schrock, R. R.; Churchill, M. R.; Wasserman, H. J. J. Am. Chem. Soc. 1982, 104, 6808. (35) Beer, S.; Hrib, C. G.; Jones, P. G.; Brandhorst, K.; Grunenberg, J.; Tamm, M. Angew. Chem., Int. Ed 2007, 46, 8890. (36) Freudenberger, J. H.; Schrock, R. R.; Churchill, M. R.; RheinGold, A. L.; Ziller, J. W. Organometallics 1984, 3, 1563. (37) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299. (38) Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284. (39) Glendening, E. D.; Reed, A. E.; Carpenter, J. E.;Weinhold, F. NBO, version 3.1; Gaussian, Inc.: Wallingford, CT. (40) Casida, M. E.; Jamorski, C.; Casida, K. C.; Salahub, D. R. J. Chem. Phys. 1998, 108, 4439. (41) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision C.02; Gaussian, Inc.: Wallingford, CT, 2003. (42) Arduengo, A. J., III; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361. (43) Boehme, C.; Frenking, G. Organometallics 1998, 17, 5801. (44) Wang, H. M. J.; Lin, I. J. B. Organometallics 1998, 17, 972. (45) Kessler, F.; Szesni, N.; Maab, C.; Hohberger, C.; Weibert, B.; Fischer, H. J. Organomet. Chem. 2007, 692, 3005. (46) Fananas-Mastral, M.; Aznar, F. Organometallics 2009, 28, 666. 9130

dx.doi.org/10.1021/jp305871m | J. Phys. Chem. A 2012, 116, 9123−9130