Article pubs.acs.org/Organometallics
Reactions of Osmium Carbyne Complexes OsCl3(CR)(PPh3)2 (R = CHCPh2, CH2Ar) with Bromine and Hydrogen Peroxide Wei Bai, Ka-Ho Lee, Wai Yiu Hung, Herman H. Y. Sung, Ian D. Williams, Zhenyang Lin,* and Guochen Jia* Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong S Supporting Information *
ABSTRACT: The reactions of the trichloro carbyne complexes OsCl3( CR)(PPh3)2 (R = CHCPh2, CH2Ar) with bromine and hydrogen peroxide were studied. Unlike monochloro carbyne complexes OsCl(CAr)(CO)(PPh3)2, the trichloro complexes OsCl3(CR)(PPh3)2 do not undergo oxidation reactions at the metal center or the metal−carbyne bond. Treatment of OsCl3(CCHCPh2)(PPh3)2 with Br2/H2O and H2O2/HCl produced OsBr3(CCHCPh2)(H2O)(PPh3) and OsCl3(CCClCPh2)(PPh3)2, respectively. Reactions of OsCl3(CCH2-C6H4-pR)(PPh3)2 (R = H, CMe3) with H2O2/HCl or H2O2 gave OsCl3{CC(O)-C6H4-p-R}(PPh3)2. Computational studies suggest that the difference in the reactivity of OsCl(CAr)(CO)(PPh3)2 and OsCl3(CR)(PPh3)2 is mainly of thermodynamic origin.
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INTRODUCTION There has been much interest in the chemistry of osmium carbyne complexes.1,2 Previous studies have led to the isolation of a number of osmium carbyne complexes with the osmium center in different formal oxidation states (e.g., OsCl( CAr)(CO)(PR3)2,3 OsCl3(CR)(PR3)34).5 It has been demonstrated that osmium carbyne complexes can undergo many interesting chemical reactions. For example, the carbyne carbons of osmium carbyne complexes can be attacked by electrophiles6 or nucleophiles7,8 to give carbene complexes. Complexes of the type LnOsCCH2R and LnOs CCHCR2 can be deprotonated to give vinylidene and allenylidene complexes.9 Complexes of the type LnOsR′( CR) (R′ = H,10 alkyl, or vinyl11) can undergo migratory insertion reactions with L′ to give carbene complexes L′LnOs(CRR′). The OsC bonds could undergo 2 + 2 cycloaddition reactions with unsaturated substrates to give metallacycles3c,12,13 and react with borohydrides to give unusual hydride or boron-containing complexes.14 Reactions of carbyne complexes with oxidizing agents are interesting as they may provide a way to modify the ligands and the oxidation state of the metal center. However, very limited work has been carried out for osmium carbyne complexes in this direction. Roper and Wright et al. reported the reactions of five-coordinate monohalo carbyne complexes Os(X)(CAr)(CO)(PPh3)2 with oxidizing agents such as O2, Cl2, and S.15 As illustrated in Scheme 1 with the reactions of OsCl(CC6H4-pR)(CO)(PPh3)2 (1), the oxidizing agents attacked the OsC bond or the metal center in these reactions. One may wonder whether carbyne complexes with the osmium in a higher formal oxidation state can also react with oxidizing agents at the OsC bond or the metal center. Until now, reactions of such carbyne complexes with oxidizing agents have only been reported for those with a formal OsC bond within a metallacycle. Xia, Zhang, and their co-workers found © XXXX American Chemical Society
Scheme 1. Oxidation Reactions of Osmium Carbyne Complexes
that osmapentalynes reacted with reagents such as ICl and Br2 at the OsC bond to produce halogen-substituted metallapentalenes (e.g., 4 reacted with Br2 to give 5, Scheme 1).16,17 In contrast, we found that osmabenzyne complexes underwent electrophilic substitution reactions with reagents such as Br2 and H2O2/HCl regioselectively at the β-carbons (e.g., 6 reacted with Br2 and H2O2/HCl to give 7 and 8, respectively, Scheme 1).18 The different regioselectivity in the reactions of carbyne complexes Os(X)(CAr)(CO)(PPh3)2 and osmapentalyne 4 as well as osmabenzyne 6 with oxidizing agents prompted us to study the reactions of typical osmium carbyne complexes Received: November 16, 2016
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DOI: 10.1021/acs.organomet.6b00860 Organometallics XXXX, XXX, XXX−XXX
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Organometallics
characteristic signal of OsC-CH at 5.04 ppm and the signal of coordinated H2O at 1.87 ppm. Complex 10 is interesting as it represents a rare example of structurally characterized osmium carbyne complexes of the type OsX3(CR)L2 with the two L-type ligands being cis to each other. Reported complexes of the type OsX3(CR)L2 (for example, OsCl3(CR)(PR′3)2,2b,4j,7c OsHCl2(CR)(PR′3)220) usually have the two L-type ligands trans to each other. A reported example of OsX3(CR)L2 complexes with two cis L ligands is fac-OsCl3(CCHCPh2)(PPh3)2.19 In principle, complex 10 could also have other isomers, for example, complex 10a, in which H2O is trans to PPh3, and complex 10b, in which H2O is trans to a bromide ligand (Chart 1). However, we have no evidence for such isomers. Our
OsX3(CAr)(PR3)2 with oxidizing agents. In this work, we report the results derived from reactions of OsCl3(CCH CPh2)(PPh3)2 and OsCl3(CCH2Ar)(PPh3)2 with Br2 and H2O2.
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RESULTS AND DISCUSSION Reactions of OsCl3(CCHCPh2)(PPh3)2 (9). The reaction of 9 with Br2 was first studied. Stirring a mixture of mer-OsCl3(CCHCPh2)(PPh3)2 (9) and Br2 in wet dichloromethane in a molar ratio of 1:20 at RT for 15 h gave a brown solution, from which the complex mer-OsBr3( CCHCPh2)(H2O)(PPh3) (10) can be isolated in 85% yield as a green solid (Scheme 2). As monitored by in situ 31P{1H} Scheme 2. Reactions of the Osmium Vinylcarbyne Complex 9 with Br2 and H2O2
Chart 1. Relative Stability of 10 and Its Isomersa
NMR, the reaction produced a mixture of species with 31P{1H} NMR signals in the region of −15.5 to −24.3 ppm if the reaction was carried out with less amounts of Br2 or in a shorter reaction time, presumably because of the formation of Br/Cl mixed complexes under these reaction conditions. The structure of 10 has been confirmed by X-ray diffraction. As shown in Figure 1, the complex can be described as a
a
The relative free energies and electronic energies (in parentheses) are given in kcal/mol.
computational studies confirmed that the isomer 10 is the most stable isomer and complex 10b is the least stable isomer. The relative stability of isomers 10, 10a, and 10b can be related to the trans influence properties of carbyne, PPh3, and bromide.21 We next studied the reaction of 9 with H2O2. No reaction was observed after a mixture of 9 with 10 equiv of H2O2 in dichloromethane was stirred at room temperature for 1 h. On the other hand, complex 9 was found to readily react with H2O2 in the presence of HCl to give the complex OsCl3(CCCl CPh2)(PPh3)2 (11) (the reaction was completed within 1 h at RT), as a result of replacement of the β-H of 9 with a chloride atom. The structure of 11 has been confirmed by X-ray diffraction (Figure 2). The complex adopts an octahedral geometry with three meridionally bound chloride ligands and with the carbyne ligand being trans to a chloride ligand. The OsC bond distance (1.746(2) Å) is slightly longer than that (1.720(4) Å) in complex 10. The C−C bond distances associated with the CCClCPh2 fragment are similar to those of CCHCPh2 in complex 10. The solid-state structure is also supported by the solution NMR data. The 31P{1H} NMR spectrum (in CDCl3) showed a singlet at −16.7 ppm. The 1H NMR spectrum did not display the characteristic CCHCPh vinyl proton signal. The 13 C{1H} spectrum displayed the OsC signal at 251.6 ppm. It is interesting to note that 9 does not undergo a bromination reaction at the β-carbon but undergoes a chlorination reaction with H2O2/HCl at the β-carbon to give 11. The observation is probably not surprising, as H2O2/HCl, which has often been used as a chlorinating agent,22 is a stronger oxidizing agent than Br2. In principle, the reaction of complex 9 with HCl/H2O2 could also give OsCl3(CCClCPh2)(H2O)(PPh3), an analogue of complex 10. Apparently, this species was not produced under our reaction conditions, probably because the reaction time (1 h) is not long enough.
Figure 1. Molecular structure of mer-OsBr3(CCHCPh2)(H2O)(PPh3) (10). The hydrogen atoms of phenyl rings are omitted for clarity. Selected bond lengths [Å] and angles [deg]: Os(1)−Br(1) 2.5181(4), Os(1)−Br(2) 2.5617(4), Os(1)−Br(3) 2.5100(4), Os(1)− P(11) 2.3532(9), Os(1)−C(1) 1.720(4), Os(1)−O(1) 2.239(2), C(1)−C(2) 1.421(5), C(2)−C(3) 1.360(5), O(1)−Os(1)−C(1) 171.62(14), Os(1)−C(1)−C(2) 169.6(3), C(1)−C(2)−C(3) 124.5(4).
distorted octahedral complex with three bromide ligands bound to Os meridionally and with the carbyne ligand being trans to the H2O ligand. The OsC bond distance (1.720(4) Å) is within the range of reported values of OsC bond distances.2b The Os−O distance (2.239(2) Å) is slightly longer than that (2.209(5) Å) in [OsCl2(CCHCPh2)(H2O)(PPh3)2]BF4.19 The solid-state structure is supported by the solution NMR data. In particular, the 31P{1H} NMR spectrum showed a singlet peak at 6.9 ppm. The 1H NMR spectrum showed the B
DOI: 10.1021/acs.organomet.6b00860 Organometallics XXXX, XXX, XXX−XXX
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Figure 2. Molecular structure of mer-OsCl3(CCClCPh2)(PPh3)2 (11). The hydrogen atoms of phenyl rings are omitted for clarity. Selected bond lengths [Å] and angles [deg]: Os(1)−Cl(2) 2.3777(5), Os(1)−Cl(3) 2.4583(5), Os(1)−Cl(4) 2.4009(5), Os(1)−P(1) 2.4366(5), Os(1)−P(2) 2.4240(5), Os(1)−C(1) 1.746(2), C(1)− C(2) 1.419(3), C(2)−C(3) 1.358(3), P(1)−Os(1)−P(2) 172.270(18), Cl(3)−Os(1)−C(1) 175.60(7), Cl(2)−Os(1)−Cl(4) 172.229(16), Os(1)−C(1)−C(2) 171.01(17), C(1)−C(2)−C(3) 126.0(2), C(1)−C(2)−Cl(1) 111.81(15).
Figure 3. Molecular structure of mer-OsCl3{CC(O)Ph}(PPh3)2 (13). The hydrogen atoms of phenyl rings are omitted for clarity. Selected bond lengths [Å] and angles [deg]: Os(1)−Cl(1) 2.3824(10), Os(1)−Cl(2) 2.4550(12), Os(1)−Cl(3) 2.3838(10), Os(1)−P(1) 2.4650(12), Os(1)−P(2) 2.4527(11), Os(1)−C(1) 1.732(4), C(1)−C(2) 1.485(6), C(2)−O(1) 1.214(6), Cl(2)− Os(1)−C(1) 178.75(15), P(1)−Os(1)−P(2) 179.40(4), Os(1)− C(1)−C(2) 172.1(4), C(1)−C(2)−O(1) 115.5(4).
Reactions of OsCl3(CCH2Ar)(PPh3)2. As mentioned in the previous section, the trichloro vinylcarbyne complex OsCl3(CCHCPh2)(PPh3)2 (9), unlike monohalo carbyne complexes OsCl(CAr)(CO)(PR3)2, does not react with Br2 and HCl/H2O2 at the metal center or the OsC bond. To further demonstrate this difference, we have studied the reactions of mer-OsCl3(CCH2Ar)(PPh3)2 with Br2 and hydrogen peroxide. Treatment of mer-OsCl3(CCH2Ph)(PPh3)2 (12) with excess Br2 (ca. 20 equiv) in dichloromethane for 15 h produced a red-colored solid, which is difficult to identify because it is insoluble in common organic solvents such as CH2Cl2, benzene, MeOH, and DMSO. Stirring a mixture of OsCl3(CCH2Ph)(PPh3)2 (12) and 10 equiv of H2O2 in dichloromethane at room temperature for 1 h produced a brownish-green solution, from which the acyl carbyne complex OsCl3{CC(O)Ph}(PPh3)2 (13) can be isolated in 57% yield (Scheme 3). Complex 13 was also produced when H2O2/HCl was used, although the reaction also produced other unidentified products under the reaction conditions.
C(2)−O(1) bond distance (1.214(6) Å) is typical for a C O double bond. The solid-state structure of 13 is fully supported by the solution NMR spectroscopic data. The 31P{1H} NMR spectrum showed a singlet at −14.8 ppm. The 1H NMR spectrum showed signals only in the aromatic region. The 13 C{1H} spectrum displayed the OsC signal at 257.4 ppm and the CO signal at 188.7 ppm. Similarly, the reaction of mer-OsCl3(CCH2-C6H4-pCMe3)(PPh3)2 (14) with H2O2 produced the analogous acylcarbyne complex OsCl3{CC(O)-C6H4-p-CMe3}(PPh3)2 (15). The structure of 15 can be readily assigned on the basis of its NMR spectroscopic data. Complexes 13 and 15 are rare examples of acylcarbyne complexes. Reported acylcarbyne complexes include Tp*(CO)2WC-C(O)Ph (formed from the reaction of Tp*(CO) 2WC-Li with PhCOCl, Tp* = hydridotris(3,5dimethylpyrazolylborate), 23 W{CC(O)Me}(OCMe 3 ) 3 (formed from the reaction of W2(OCMe3)6 with EtC CC(O)Me),24 and OsCl3{CC(O)Ph}(PCy3)2 (formed from the reaction of Os(C)(PCy3)2Cl2 with PhCOCl).25 It is noted that the carbyne complexes OsCl3(CCH2C6H4-p-R)(PPh3)2 (12, R = H; 14, R = CMe3) readily react with H2O2 at the β-carbon to give acyl carbyne complexes, while the vinyl carbyne complex OsCl3(CCHCPh2)(PPh3)2 (9) does not react with H2O2 under a similar reaction condition. The difference may be related to the fact that the βcarbons of complexes 12 and 14 are benzylic carbons, while the β-carbon of complex 9 is a vinylic carbon. It is known that allylic and benzylic C−H bonds can be oxidized preferentially to give carbonyl compounds (e.g., 1-indene can be oxidized by tert-butyl hydroperoxide to give indenone26). To the best of our knowledge, the reactions of 12 and 14 with H2O2 to give 13 and 15, respectively, are the first examples of oxidation reactions of carbyne complexes to give acylcarbyne complexes. In fact, oxidation of substituents on carbyne ligands has been rarely observed previously, although a number of oxidation reactions of carbyne complexes at the metal centers27
Scheme 3. Reactions of OsCl3(CCH2Ar)(PPh3)2 with H2O2
The structure of complex 13 has been confirmed by a singlecrystal X-ray diffraction study. As shown in Figure 3, the complex has a coordination sphere similar to that of 11. The OsC bond length (1.732(4) Å) is between those in complexes 10 (1.720(4) Å) and 11 (1.746(2) Å). The C
DOI: 10.1021/acs.organomet.6b00860 Organometallics XXXX, XXX, XXX−XXX
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Organometallics or the metal−carbyne bonds28 are known. The only example we are aware of is the sulfuration of the PPh2 substituent in Tp*(CO)2WCPPh2 to afford a mixture of the thiophosphorylcarbyne complex Tp*(CO)2W{CP(S)Ph2} and the thioacyl complex Tp*(CO)2W{η2-SCP(S)Ph2}.29 Comment on the Reactions at the OsC Bonds. It is interesting to note that the complex OsCl{C(-p-tolyl)}(CO)(PPh3)2 reacts with Cl2 at the OsC bond to give the carbene complex OsCl2{CCl(-p-tolyl)}(CO) (PPh3)2 (2), but the OsC bonds of the osmabenzyne 6 and the carbyne complexes 9, 12, and 14 remain intact in their reactions with Br2. To understand why the OsC bonds in these complexes behave differently in the reactions with halogens, we have studied the thermodynamics of the addition of halogens (Br2 or Cl2) to the OsC bonds of model complexes 16 (a model for OsCl{C(-p-tolyl)}(CO) (PPh3)2), 18 (a model for 6), 20 (a model for 9), and 22 (a model for 12 and 14) by computational chemistry (see Scheme 4 for their structures).
larger than those of osmabenzynes (with an OsC bond within a six-membered ring). Comment on the Reactions of the Osmabenzyne Complex 6 and the Vinylcarbyne Complex 9. Subtle differences were also noted for the reactions of the osmabenzyne complex 6 and the vinylcarbyne complex 9 with bromine and H2O2/HCl. For the reactions involving Br2, the β-H was not replaced by bromide in the reaction of 9 but was replaced by bromide in the reaction of 6. In the reaction of 6 with H2O2/HCl, the β-H was replaced by Cl and an O atom is added across the OsC bond to give chloro-substituted metallabenzene 8 (see Scheme 1). In the reaction of 9 with H2O2/HCl, only the β-H was replaced by Cl to give the chlorosubstituted vinylcarbyne complex 11 (see Scheme 2). Our computational results suggest that the difference in the reactivity of 6 and 9 toward Br2 is also of thermodynamic origin. As shown in Scheme 5, bromination of osmabenzyne 18 Scheme 5. Calculated Free Energy Changes for the Halogenation and Oxygenation of Complexes 18 and 20
Scheme 4. Calculated Free Energy Changes for the Halogenation of Complexes 16, 18, 20, and 22
Consistent with the experimental observations, chlorination of 16 to give the carbene complex 17 was found to be thermodynamically favorable (by 62.63 kcal/mol), while brominations of 20 and 22 to give the corresponding carbene complexes are thermodynamically unfavorable (by 23.76 and 21.32 kcal/mol, respectively; see Scheme 4). The opposite thermodynamics can be related to the fact that the formal oxidation state of the complex 16 is lower than those of complexes 20 and 22. The bromination of the osmabenzyne 18 to give the metallabenzene complex 19 is also thermodynamically unfavorable. However, the endothermicity (by 6.13 kcal/mol) is less than those for the reactions of 20 and 22, probably because 18 has ring strain. We noted that osmapentalynes such as 4 can react with reagents such as ICl and Br2 at the OsC bond to produce the halogen-substituted metallapentalenes.16 The result is probably not surprising, as osmapentalynes (with a OsC bond within a five-membered ring) have a ring strain
(a model for 6) to give 24 is thermodynamically favored by 4.83 kcal/mol, while bromination of the vinylcarbyne complex 20 (a model for 9) to give 25 is essentially thermodynamically neutral. The difference can be related to the fact that complex 24 is an aromatic matallacycle that is expected to have a C−Br bond stronger than that in the vinylcarbyne complex 25. It has been reported that the bond energies of the C−Br bonds in D
DOI: 10.1021/acs.organomet.6b00860 Organometallics XXXX, XXX, XXX−XXX
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Reaction of mer-OsCl3(CCHCPh2)(PPh3)2 (9) with Br2. Br2 (0.10 mL, 1.96 mmol) was added to a solution of mer-OsCl3( CCHCPh2)(PPh3)2 (9) (100 mg, 0.0988 mmol) in dichloromethane (10 mL). The mixture was stirred at room temperature for 15 h to give a brown solution. The volatiles were completely removed under vacuum, and the residue was stirred with acetone (3 mL) for 30 min to give a green precipitate, which was collected by filtration, washed with acetone (3 mL), diethyl ether (2 × 5 mL), and hexane (2 × 5 mL), and dried under vacuum to give 10 as a green solid. Yield: 76 mg, 85.3%. 31P{1H} NMR (162.0 MHz, CDCl3): δ 6.9 (s). 1H NMR (400.1 MHz, CDCl3): δ 1.87 (s, 2H, H2O), 5.04 (s, 1H), 7.40−7.24 (m, 12H), 7.67−7.49 (m, 11H), 7.93 (d, 1JHH = 7.2 Hz, 2H). Due to its poor solubility in CDCl3 or CD2Cl2, it is difficult to collect its 13 C{1H} NMR. Anal. Calcd for C35H28Br3OPOs: C, 43.97, H, 3.13. Found: C, 43.74, H, 3.24. Reaction of mer-OsCl3(CCHCPh2)(PPh3)2 (9) with HCl/ H2O2. HCl (1.0 M in diethyl ether, 1.0 mL, 1.0 mmol) and H2O2 (30 wt %, 0.10 mL, 0.979 mmol) were added to a solution of merOsCl3(CCHCPh2)(PPh3)2 (9) (100 mg, 0.0988 mmol) in dichloromethane (10 mL). The mixture was stirred at room temperature for 1 h to give a green solution. The volatiles were completely removed under vacuum, and the greenish residue was washed with diethyl ether (2 × 5 mL) and hexane (2 × 5 mL) and dried under vacuum to give 11 as a green solid. Yield: 96 mg, 92.8%. Caution! Hydrogen peroxide is potentially hazardous and explosive. It should be handled with special care and precautions. A safer procedure to isolate the product is to wash the crude reaction mixture with water to separate the excess H2O2 before removing the volatiles under vacuum. 31 1 P{ H} NMR (162.0 MHz, CDCl3): δ −16.7 (s). 1H NMR (400.1 MHz, CDCl3): δ 6.65 (d, 1JHH = 3.8 Hz, 2H), 6.81 (d, 1JHH = 3.6 Hz, 2H), 7.55−7.17 (m, 24H), 7.75−7.69 (m, 12H). 13C{1H} NMR (100.6 MHz, CDCl3): δ 251.6 (t, 2JPC = 11.6 Hz, OsC), 157.2 (s, CPh2), 138.7−127.6 (m). Anal. Calcd for C51H40Cl4P2Os: C, 58.51, H, 3.85. Found: C, 58.76, H, 4.06. Reaction of mer-OsCl3(CCH2Ph)(PPh3)2 (12) with H2O2. H2O2 (30 wt %, 0.35 mL, 3.43 mmol) was added to a solution of merOsCl3(CCH2Ph)(PPh3)2 (12) (300 mg, 0.325 mmol) in dichloromethane (10 mL). The mixture was stirred at room temperature for 1 h to give a brownish-green solution. The volatiles were completely removed under vacuum [please note the caution mentioned above], and the residue was redissolved in 3 mL of dichloromethane. Diethyl ether (10 mL) was then added slowly to give a greenish-yellow precipitate, which was collected by filtration, washed with diethyl ether (2 × 3 mL) and hexane (3 mL), and dried under vacuum to give 13 as a yellow solid. Yield: 180 mg, 59%. 31P{1H} NMR (121.5 MHz, CD2Cl2): δ −14.8 (s). 1H NMR (300.1 MHz, CD2Cl2): δ 7.28−7.83 (m, 35H). 13C{1H} NMR (75.5 MHz, CD2Cl2): δ 257.4 (t, 2JPC = 12.0 Hz, OsC), 188.7 (s, CO), 135.4−128.1 (m). Anal. Calcd for C44H35Cl3OP2Os: C, 56.32, H, 3.76. Found: C, 56.18, H, 4.00. Preparation of mer-OsCl3(CCH2-C6H4-p-CMe3)(PPh3)2 (14). HCC-C6H4-p-CMe3 (0.35 mL, 1.94 mmol) and HCl (1.0 M in diethyl ether, 1.0 mL, 1.0 mmol) were added to a solution of OsCl2(PPh3)3 (500 mg, 0.477 mmol) in toluene (15 mL). The mixture was stirred at room temperature for 4 h to give a brown solution and yellow solid. The yellow solid was collected by filtration, washed with diethyl ether (2 × 10 mL) and methanol (2 × 5 mL), and dried under vacuum. Yield: 265 mg, 56.6%. 31P{1H} NMR (162.0 MHz, CDCl3): δ −12.2 (s). 1H NMR (400.1 MHz, CDCl3): δ 1.27 (s, 9H, tBu), 1.74 (br s, 2H, CH2), 6.38 (d, 1JHH = 4.2 Hz, 2H), 7.07 (d, 1 JHH = 4.2 Hz, 2H), 7.28−7.36 (m, 18H), 7.79−7.83 (m, 12H). 13 C{1H} NMR (100.6 MHz, CDCl3): δ 279.5 (t, 2JPC = 12.0 Hz, Os C), 150.8−122.6 (m), 56.6 (s, CH2), 34.7 (s, CMe3), 31.5 (s, CMe3). Anal. Calcd for C48H45Cl3P2Os: C, 58.80, H, 4.63. Found: C, 58.63, H, 4.88. Reaction of mer-OsCl3(CCH2-C6H4-p-CMe3)(PPh3)2 (14) with H2O2. H2O2 (30 wt %, 0.30 mL, 2.94 mmol) was added to a solution of mer-OsCl3(CCH2-C6H4-p-CMe3)(PPh3)2 (14) (300 mg, 0.306 mmol) in dichloromethane (10 mL). The mixture was stirred at room temperature for 1 h to give a brownish-green solution. The volatiles were completely removed under vacuum, and the residue was
PhBr and CH 2 CHBr are 82.6 and 79.5 kcal/mol, respectively.30 In the halogenation of organic compounds with H2O2/HCl, hypochlorous acid (HOCl) has been suggested as the most probable active species,22 although other chlorinating species, for example, Cl2, Cl2O, and H2OCl+, have also been considered.22,31,32 Assuming that the active species is also HOCl, chlorination of the vinylcarbyne complex 20 (a model for 9) to give the model chlorinated vinylcarbyne complex 27 (a model for 11) was calculated to be thermodynamically favorable, in agreement with the experimental observation that complex 11 can be isolated from the reactions of 9 with H2O2/ HCl. As expected, the chlorination of the model osmabenzyne complex 18 with HOCl to give the chloronated osmabenzyne complex 26 was also found to be thermodynamically favorable. Like the reactions of Br2, the chlorination of the osmabenzyne complex 18 with HOCl is also thermodynamically more favorable than the reaction of the vinylcarbyne complex 20 with HOCl. Our computational studies also revealed that complex 26 can react with HOCl to give the oxygenated product 28 (a model for 8) exothermically (by 56.59 kcal/mol; see Scheme 5), in agreement with the experimental observation that complex 8 can be isolated from the reactions of 6 with H2O2/HCl. The reaction of complex 27 with HOCl to give the oxygenated product 29 is also calculated to be thermodynamically favorable, although the exothermicity is less (by 22.44 kcal/ mol) than that of the reaction of 26 (see Scheme 5). The higher exothermicity of the reaction of 26 is likely caused by the fact that complex 26 is a strained molecule, while complex 27 is not. Our computational results suggest that the reaction of complex 9 with H2O2/HCl to produce an oxygenated species analogous to 29 is thermodynamically feasible, although we have no experimental evidence for such species. The calculated results imply that the different outcomes in the reactions of 6 and 9 with H2O2/HCl are likely related to kinetics. Summary. Unlike the monochloro carbyne complexes OsCl(CAr)(CO)(PPh3)2, the trichloro carbyne complexes OsCl3(CR)(PPh3)2 do not undergo oxidation reactions at the metal center and the metal−carbyne bond. Reactions of OsCl3(CCHCPh2)(PPh3)2 with Br2/H2O and H2O2/HCl produced OsBr3(CCHCPh2)(H2O)(PPh3) and OsCl3( CCClCPh2)(PPh3)2, respectively. Reactions of OsCl3( CCH2-C6H4-p-R)(PPh3)2 (R = H, CMe3) with H2O2/HCl or H2O2 give OsCl3{CC(O)-C6H4-p-R}(PPh3)2. Subtle differences were also noted for the outcomes of the reactions of the osmabenzyne complexes and the vinylcarbyne complex OsCl3(CCHCPh2)(PPh3)2 with bromine and H2O2/HCl.
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EXPERIMENTAL SECTION
All manipulations were carried out under a nitrogen atmosphere using standard Schlenck techniques unless otherwise stated. Solvents were distilled under nitrogen from sodium benzophenone (hexane, ether), sodium (toluene), or calcium hydride (CH2Cl2). Other reagents were used as purchased from Aldrich Chemical Co. USA. Microanalyses were performed by M-H-W Laboratories (Phoenix, AZ, USA). The complexes mer-OsCl3(CCHCPh2)(PPh3)219 and mer-OsCl3( CCH2Ph)(PPh3)233 were prepared according to literature methods. 1 H, 13C{1H}, and 31P{1H} spectra were collected on a Bruker ARX400 spectrometer (400 MHz) or a Bruker ARX-300 spectrometer (300 MHz). 1H and 13C NMR shifts are relative to TMS, and 31P chemical shifts relative to 85% H3PO4. E
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redissolved in 3 mL of dichloromethane [please note the caution mentioned above]. Diethyl ether (10 mL) was then added slowly to give a greenish-yellow precipitate, which was collected by filtration, washed with diethyl ether (2 × 3 mL) and hexane (3 mL), and dried under vacuum to give 15 as a yellow solid. Yield: 218 mg, 72.0%. 31 1 P{ H} NMR (162.0 MHz, C6D6): δ −14.9 (s). 1H NMR (400.1 MHz, C6D6): δ 1.02 (s, 9H, tBu), 6.80−7.04 (m, 20H), 7.87 (d, 1JHH = 14.2 Hz, 2H), 8.24−8.28 (m, 12H). 13C{1H} NMR (100.6 MHz, C6D6): δ 257.4 (t, 2JPC = 11.7 Hz, OsC), 188.8 (s, CO), 159.3− 126.2 (m), 35.6 (s, CMe3), 31.2 (s, CMe3). Anal. Calcd for C48H43Cl3OP2Os·1.5H2O: C, 56.19, H, 4.71. Found: C, 56.44, H, 4.54. X-ray Crystallography. Single crystals of 10, 11, and 13 suitable for X-ray diffraction were grown from CH2Cl2 solutions layered with hexane (for 10 and 11) or with diethyl ether and hexane (for 13). Intensity data of 10, 11, and 13 were collected on a Rigaku-Oxford Diffraction SuperNova diffractometer at 100 K (for 10 and 11) or at 173 K (for 13). Diffraction data were processed using the CrysAlisPro software (version 1.171.35.19). Empirical absorption corrections were performed using spherical harmonics, implemented in the SCALE3 ABSPACK scaling algorithm in the CrysAlisPro software suite. Structure solution and refinement for all compounds were performed using the Olex2 software package (which embedded SHELXL).34,35 All the structures were solved by direct methods, expanded by difference Fourier syntheses, and refined by full matrix least-squares on F2. All non-hydrogen atoms were refined anisotropically with a riding model for the hydrogen atoms except as noted separately. Further crystallographic details are summarized in Table S1. Computational Details. All structures were optimized without any constraint at the B3LYP level of density functional theory.36 The standard 6-31G* basis set was used for O, C, and H atoms (unless specified), and the 6-31G** basis set was used for the H atom involved in bond-breaking and -forming processes,37 where the effective core potentials of Lanl2dz were used to describe Os, Br, Cl, and P atoms,38 with polarization functions for Os (ζ(f) = 0.886), Br (ζ(d) = 0.428), Cl (ζ(d) = 0.640), and P (ζ(d) = 0.387) being added.39 Frequency calculations were also performed at the same level of theory to identify all the stationary points as minima (zero imaginary frequency) or transition states (one imaginary frequency), as well as to provide free energies at 298.15 K. To reduce the overestimation of the entropy contribution in the gas-phase results, corrections of −2.6 kcal/mol in free energies were made for 2:1 transformations.40 This free energy correction was applied in a number of earlier computational studies.41 All the calculations were performed with the Gaussian 03 software package.42
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ACKNOWLEDGMENTS This work was supported by the Hong Kong Research Grants Council (Project Nos. 602113, CUHK7/CRF/12G-2, 16321516). We also thank Dr. S. M. Yiu (at the Department of Biology and Chemistry, City University of Hong Kong) for his assistance in the X-ray studies of complex 13.
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REFERENCES
(1) For general reviews of the chemistry of carbyne complexes: (a) Kim, H. S.; Angelici, R. J. Adv. Organomet. Chem. 1987, 27, 51− 111. (b) Mayr, A.; Hoffmeister, H. Adv. Organomet. Chem. 1991, 32, 227−324. (c) Mayr, A.; Ahn, S. Adv. Trans. Metal Coord. Chem. 1996, 1, 1−103. (2) For reviews on osmium carbyne complexes, see: (a) Bolano, T.; Esteruelas, M. A.; Oñate, E. J. Organomet. Chem. 2011, 696, 3911− 3923. (b) Jia, G. Coord. Chem. Rev. 2007, 251, 2167−2187. (c) Esteruelas, M. A.; López, A. M.; Olivan, M. Coord. Chem. Rev. 2007, 251, 795−840. (d) Gallop, M. A.; Roper, W. R. Adv. Organomet. Chem. 1986, 25, 121−198. (3) Recent examples: (a) Buil, M. L.; Cardo, J. J. F.; Esteruelas, M. A.; Oñate, E. J. Am. Chem. Soc. 2016, 138, 9720−9728. (b) Esteruelas, M. A.; González, A. I.; López, A. M.; Oñate, E. Organometallics 2003, 22, 414−425. (c) Clark, G. R.; Cochrane, C. M.; Marsden, K.; Roper, W. R.; Wright, L. J. J. Organomet. Chem. 1986, 315, 211−230. (4) Recent examples: (a) Casanova, N.; Esteruelas, M. A.; Gulías, M.; Larramona, C.; Mascareñas, J. L.; Oñate, E. Organometallics 2016, 35, 91−99. (b) Wen, T.; Lee, K.-H.; Chen, J.; Hung, W. Y.; Bai, W.; Li, H.; Sung, H. H. Y.; Williams, I. D.; Lin, Z.; Jia, G. Organometallics 2016, 35, 1514−1525. (c) Zhu, C.; Yang, Y.; Wu, J.; Luo, M.; Fan, J.; Zhu, J.; Xia, H. Angew. Chem., Int. Ed. 2015, 54, 7189−7192. (d) Bajo, S.; Esteruelas, M. A.; López, A. M.; Oñate, E. Organometallics 2014, 33, 4057−4066. (e) An, R.; Li, T.; Wen, T. Chin. J. Org. Chem. 2013, 33, 1697−1708. (f) Collado, A.; Esteruelas, M. A.; Gulías, M.; Mascareñas, J. L.; Oñate, E. Organometallics 2012, 31, 4450−4458. (g) CastroRodrigo, R.; Esteruelas, M. A.; López, A. M.; Oñate, E. Organometallics 2012, 31, 1991−2000. (h) Collado, A.; Esteruelas, M. A.; Oñate, E. Organometallics 2011, 30, 1930−1941. (i) Collado, A.; Esteruelas, M. A.; López, F.; Mascareñas, J. L.; Oñate, E.; Trillo, B. Organometallics 2010, 29, 4966−4974. (j) Richter, B.; Werner, H. Organometallics 2009, 28, 5137−5141. (k) Bolano, T.; Collado, A.; Esteruelas, M. A.; Oñate, E. Organometallics 2009, 28, 2107−2111. (l) Berthoud, R.; Rendon, N.; Blanc, F.; Solans-Monfort, X.; Coperet, C.; Eisenstein, O. Dalton Trans. 2009, 30, 5879−5886. (m) Lee, J.-H.; Pink, M.; Smurnyy, Y. D.; Caulton, K. G. J. Organomet. Chem. 2008, 693, 1426− 1438. (n) Castarlenas, R.; Esteruelas, M. A.; Oñate, E. Organometallics 2007, 26, 2129−2132. (5) It is not easy to define the exact oxidation state of the metal center in a metal carbyne complex. The assignment of the oxidation state of a metal center in a metal carbyne complex LnMCR can be ambiguous, since the complex can be regarded as either a complex made of LnM and CR, in which the latter can be viewed as either an LX or X3 type ligand, or a complex made of LnM− and CR+, depending on metals and ligands. See: Crabtree, R. H. The Organometallic Chemistry of the Transition Metals, 3rd ed.; John Wiley & Sons: New York, 2001; pp 308−309. For example, the oxidation state of Os in OsCl3(CR)(PPh3)2 can be assigned as either +4, +6, or +2 depending on how we view the interaction between the osmium center and the carbyne ligand. For the sake of easy discussion, the oxidation state of Os in carbyne complexes discussed in this work is derived by assuming all the carbyne ligands are of the same valence. (6) (a) Baker, L. J.; Clark, G. R.; Rickard, C. E. F.; Roper, W. R.; Woodgate, S. D.; Wright, L. J. J. Organomet. Chem. 1998, 551, 247− 259. (b) Roper, W. R. J. Organomet. Chem. 1986, 300, 167−190. (7) Recent examples: (a) Zhu, C.; Luo, M.; Zhu, Q.; Zhu, J.; Schleyer, P. v. R.; Wu, J. I.-C.; Lu, X.; Xia, H. Nat. Commun. 2014, 5, 3265. (b) Zhu, C.; Li, S.; Luo, M.; Zhou, X.; Niu, Y.; Lin, M.; Zhu, J.; Cao, Z.; Lu, X.; Wen, T.; Xie, Z.; Schleyer, P. v. R.; Xia, H. Nat. Chem. 2013, 5, 698−703. (c) Chen, J.; Sung, H. H. Y.; Williams, I. D.; Jia, G.
ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.6b00860. Crystallographic data of complexes 10, 11, and 13; NMR spectra (PDF) Crystallographic data of complexes 10, 11, and 13 (CIF) Cartesian coordinates of all the calculated structures (XYZ)
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Article
AUTHOR INFORMATION
Corresponding Authors
*E-mail (Z. Lin):
[email protected]. *E-mail (G. Jia):
[email protected]. ORCID
Ka-Ho Lee: 0000-0002-8435-4986 Zhenyang Lin: 0000-0003-4104-8767 Guochen Jia: 0000-0002-4285-8756 Notes
The authors declare no competing financial interest. F
DOI: 10.1021/acs.organomet.6b00860 Organometallics XXXX, XXX, XXX−XXX
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Organometallics Organometallics 2011, 30, 6159−6165. (d) Chen, H.; Liu, R.; Myers, W. H.; Harman, W. D. J. Am. Chem. Soc. 1998, 120, 509−520. (8) Nucleophiles may also attack aromatic rings attached to the carbyne carbons. (a) Roper, W. R.; Waters, J. M.; Wright, L. J. J. Organomet. Chem. 1980, 201, C27−C30. (b) Baker, L. J.; Rickard, C. F.; Roper, W. R.; Woodgate, S. D.; Wright, L. J. J. Organomet. Chem. 1998, 565, 153−158. (9) See for example: (a) Bolano, T.; Castarlenas, R.; Esteruelas, M. A.; Oñate, E. J. Am. Chem. Soc. 2006, 128, 3965−3973. (b) Baya, M.; Esteruelas, M. A. Organometallics 2002, 21, 2332−2335. (c) Barrio, P.; Esteruelas, M. A.; Oñate, E. Organometallics 2002, 21, 2491−2503. (d) Baya, M.; Crochet, P.; Esteruelas, M. A.; Gutiérrez-Puebla, E.; López, A. M.; Modrego, J.; Oñate, E.; Vela, N. Organometallics 2000, 19, 2585−2596. (e) Esteruelas, M. A.; García-Yebra, C.; Oliván, M.; Oñate, E.; Tajada, M. A. Organometallics 2000, 19, 5098−5106. (f) Buil, M. L.; Eisenstein, O.; Esteruelas, M. A.; García-Yebra, C.; Gutiérrez-Puebla, E.; Oliván, M.; Oñate, E.; Ruiz, N.; Tajada, M. A. Organometallics 1999, 18, 4949−4959. (10) See for examples: (a) Buil, M. L.; Cardo, J. J. F.; Esteruelas, M. A.; Oñate, E. Organometallics 2016, 35, 2171−2173. (b) Zhou, X.; He, X.; Lin, J.; Zhuo, Q.; Chen, Z.; Zhang, H.; Wang, J.; Xia, H. Organometallics 2015, 34, 1742−1750. (c) Liu, B.; Zhao, Q.; Wang, H.; Chen, J.; Cao, X.; Cao, Z.; Xia, H. Chin. J. Chem. 2012, 30, 2158− 2168. (d) Liu, B.; Xie, H.; Wang, H.; Wu, L.; Zhao, Q.; Chen, J.; Wen, T. B.; Cao, Z.; Xia, H. Angew. Chem., Int. Ed. 2009, 48, 5461−5464. (e) Buil, M. L.; Esteruelas, M. A.; Garces, K.; Oñate, E. Organometallics 2009, 28, 5691−5696. (f) He, G.; Zhu, J.; Hung, W. Y.; Wen, T. B.; Sung, H. H.-Y.; Williams, I. D.; Lin, Z.; Jia, G. Angew. Chem., Int. Ed. 2007, 46, 9065−9068. (g) Bolaño, T.; Castarlenas, R.; Esteruelas, M. A.; Oñate, E. J. Am. Chem. Soc. 2007, 129, 8850−8859. (h) Bolaño, T.; Castarlenas, R.; Esteruelas, M. A.; Oñate, E. Organometallics 2007, 26, 2037−2041. (i) Lee, J. H.; Pink, M.; Caulton, K. G. Organometallics 2006, 25, 802−804. (j) Bolaño, T.; Castarlenas, R.; Esteruelas, M. A.; Modrego, J.; Oñate, E. J. Am. Chem. Soc. 2005, 127, 11184−11195. (k) Jacobsen, H. J. Organomet. Chem. 2003, 674, 50−55. (l) Baya, M.; Esteruelas, M. A.; Oñate, E. Organometallics 2002, 21, 5681−5684. (m) Baya, M.; Esteruelas, M. A.; Oñate, E. Organometallics 2001, 20, 4875−4886. (n) Caulton, K. G. J. Organomet. Chem. 2001, 617−618, 56−64. (o) Spivak, G. J.; Caulton, K. G. Organometallics 1998, 17, 5260−5266. (p) Spivak, G. J.; Coalter, J. N.; Oliván, M.; Eisenstein, O.; Caulton, K. G. Organometallics 1998, 17, 999−1001. (11) (a) Chen, J.; Shi, C.; Sung, H. H. Y.; Williams, I. D.; Lin, Z.; Jia, G. Angew. Chem., Int. Ed. 2011, 50, 7295−7299. (b) Bolano, T.; Castarlenas, R.; Esteruelas, M. A.; Oñate, E. Organometallics 2008, 27, 6367−6370. (c) Castro-Rodrigo, R.; Esteruelas, M. A.; López, A. M.; Oñate, E. Organometallics 2008, 27, 3547−3555. (d) Barrio, P.; Esteruelas, M. A.; Oñate, E. J. Am. Chem. Soc. 2004, 126, 1946−1947. (e) Castarlenas, R.; Esteruelas, M. A.; Oñate, E. Organometallics 2001, 20, 3283−3292. (12) Cycloaddition reactions of alkynes with an osmapentalyne that contains a strained OsC bond have been reported recently: Zhu, C.; Yang, Y.; Luo, M.; Yang, C.; Wu, J.; Chen, L.; Liu, G.; Wen, T.; Zhu, J.; Xia, H. Angew. Chem., Int. Ed. 2015, 54, 6181−6185. (13) For an example of [2 + 2] cycloaddition reaction of osmium carbyne complexes with alkenes, see: Esteruelas, M. A.; González, A. I.; López, A. M.; Oñate, E. Organometallics 2004, 23, 4858−4870. (14) (a) Buil, M. L.; Cardo, J. J. F.; Esteruelas, M. A.; Fernandez, I.; Oñate, E. Inorg. Chem. 1993, 32, 5062−5070. (b) Buil, M. L.; Cardo, J. J. F.; Esteruelas, M. A.; Fernández, I.; Oñate, E. Organometallics 2014, 33, 2689−2692. (c) Buil, M. L.; Cardo, J. J. F.; Esteruelas, M. A.; Fernández, I.; Oñate, E. Organometallics 2015, 34, 547−550. (15) (a) Clark, G. R.; Marsden, K.; Roper, W. R.; Wright, L. J. J. Am. Chem. Soc. 1980, 102, 6570−6571. (b) Clark, G. R.; Edmonds, N. R.; Pauptit, R. A.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Organomet. Chem. 1983, 244, C57−C60. (16) Luo, M.; Zhu, C.; Chen, L.; Zhang, H.; Xia, H. Chem. Sci. 2016, 7, 1815−1818. (17) Xia and his co-workers have reported the reactions of the hydrido butenylcarbyne complex [OsH{CC-(PPh3)CH(Et)}-
(PPh3)2Cl2]BF4 with air or H2O2. However, the oxidation reaction occurs after the carbyne complex is converted to carbene or vinyl complexes. See: (a) Chen, J.; Zhang, C.; Xie, T.; Wen, T. B.; Zhang, H.; Xia, H. Organometallics 2013, 32, 3993−4001. (b) Chen, J.; Huang, Z. A.; Hua, Y.; Zhang, H.; Xia, H. Organometallics 2015, 34, 340−347. (18) (a) Hung, W. Y.; Liu, B.; Shou, W.; Wen, T. B.; Shi, C.; Sung, H. H.-Y.; Williams, I. D.; Lin, Z.; Jia, G. J. Am. Chem. Soc. 2011, 133, 18350−18360. (b) Wen, T. B.; Ng, S. M.; Hung, W. Y.; Zhou, Z. Y.; Lo, M. F.; Shek, L. Y.; Williams, I. D.; Lin, Z.; Jia, G. J. Am. Chem. Soc. 2003, 125, 884−885. (19) Wen, T. B.; Zhou, Z. Y.; Lo, M. F.; Williams, I. D.; Jia, G. Organometallics 2003, 22, 5217−5225. (20) See for example: (a) Liu, B.; Wang, H.; Xie, H.; Zeng, B.; Chen, J.; Tao, J.; Wen, T. B.; Cao, Z.; Xia, H. Angew. Chem., Int. Ed. 2009, 48, 5430−5434. (b) Ferrando, G.; Coalter, J. N., III; Gérard, H.; Huang, D.; Eisenstein, O.; Caulton, K. G. New J. Chem. 2003, 27, 1451−1462. (c) Ferrando, G.; Gérard, H.; Eisenstein, O.; Caulton, K. G. Inorg. Chem. 2002, 41, 6440−6449. (d) Ferrando, G.; Gérard, H.; Spivak, G. J.; Coalter, J. N., III; Huffman, J. C.; Eisenstein, O.; Caulton, K. G. Inorg. Chem. 2002, 41, 6610−6621. (e) Werner, H.; Jung, S.; Weberndorfer, B.; Wolf, J. Eur. J. Inorg. Chem. 1999, 1999, 951− 957. (f) Weber, B.; Steinert, P.; Windmueller, B.; Wolf, J.; Werner, H. J. Chem. Soc., Chem. Commun. 1994, 22, 2595−2596. (g) Espuelas, J.; Esteruelas, M. A.; Lahoz, F. J.; Oro, L. A.; Ruiz, N. J. Am. Chem. Soc. 1993, 115, 4683−4689. (21) For general review, see: (a) Shustorovich, E. M.; Poraikoshits, M. A.; Buslaev, Y. A. Coord. Chem. Rev. 1975, 17, 1−98. For a discussion on the trans influence of carbyne ligands, see: (b) Zhang, L.; Gamasa, M. P.; Gimeno, J.; Carbajo, R. J.; López-Ortiz, F.; Lanfranchi, M.; Tiripicchio, A. Organometallics 1996, 15, 4274−4284. (22) Podgoršek, A.; Zupan, M.; Iskra, J. Angew. Chem., Int. Ed. 2009, 48, 8424−8450. (23) Enriquez, A. E.; White, P. S.; Templeton, J. L. J. Am. Chem. Soc. 2001, 123, 4992−5002. (24) Listemann, M. L.; Schrock, R. R. Organometallics 1985, 4, 74− 83. (25) Stewart, M. H.; Johnson, M. J. A.; Kampf, J. W. Organometallics 2007, 26, 5102−5110. (26) For example: Zarghani, M.; Akhlaghinia, B. RSC Adv. 2016, 6, 38592−38601. (27) For oxidation of group 6 d2 M(IV) carbyne complexes at the metal centers, see for example: (a) Haberlag, B.; Freytag, M.; Daniliuc, C. G.; Jones, P. G.; Tamm, M. Angew. Chem., Int. Ed. 2012, 51, 13019−13022. (b) Anderson, S.; Cook, D. J.; Hill, A. F.; Malget, J. M.; White, A. J. P.; Williams, D. J. Organometallics 2004, 23, 2552−2557. (c) Furno, F.; Fox, T.; Schmalle, H. W.; Berke, H. Organometallics 2000, 19, 3620−3630. (d) Mayr, A.; Ahn, S. Inorg. Chim. Acta 2000, 300−302, 406−413. (e) Woodworth, B. E.; White, P. S.; Templeton, J. L. J. Am. Chem. Soc. 1998, 120, 9028−9033. (f) Ahn, S.; Mayr, A. J. Am. Chem. Soc. 1996, 118, 7408−7409. (g) Lungwitz, B.; Filippou, A. C. J. Organomet. Chem. 1995, 498, 91−107. (h) Klaeui, W.; Hardt, T.; Schulte, H.; Hamers, H. J. Organomet. Chem. 1995, 498, 63−71. (i) Filippou, A. C.; Hofmann, P.; Kiprof, P.; Schmidt, H. R.; Wagner, C. J. Organomet. Chem. 1993, 459, 233−247. (j) Filippou, A. C.; Gruentleitner, W.; Volkl, C.; Kiprof, P. Angew. Chem., Int. Ed. Engl. 1991, 30, 1167−1169. (k) Filippou, A. C.; Fischer, E. O.; Gruenleitner, W. J. Organomet. Chem. 1990, 386, 333−47. (l) Filippou, A. C.; Fischer, E. O. J. Organomet. Chem. 1990, 382, 143−156. (m) Filippou, A. C. Polyhedron 1989, 8, 1285−1291. (n) Filippou, A. C.; Fischer, E. O. J. Organomet. Chem. 1988, 349, 367−374. (o) Filippou, A. C.; Fischer, E. O.; Alt, H. G. J. Organomet. Chem. 1988, 344, 215−225. (p) Filippou, A. C.; Fischer, E. O. J. Organomet. Chem. 1988, 341, C35−C38. (q) Filippou, A. C.; Fischer, E. O.; Okuda, J. J. Organomet. Chem. 1988, 339, 309−321. (r) Mayr, A.; Asaro, M. F.; Kjelsberg, M. A.; Lee, K. S.; Van Engen, D. Organometallics 1987, 6, 432−434. (s) Mayr, A.; McDermott, G. A. J. Am. Chem. Soc. 1986, 108, 548−549. For oxidation of d2 Re(V) and d1 Re(VI) carbyne complexes, see: (t) Herrmann, W. A.; Felixberger, J. G
DOI: 10.1021/acs.organomet.6b00860 Organometallics XXXX, XXX, XXX−XXX
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Organometallics K.; Anwander, R.; Herdtweck, E.; Kiprof, P.; Riede, J. Organometallics 1990, 9, 1434−1443. (u) Xue, W. M.; Chan, M. C. W.; Mak, T. C.; Che, C. M. Inorg. Chem. 1997, 36, 6437−6439. For oxidation of d4 Ru(IV) carbyne complexes, see: (v) Clark, G. R.; Cochrane, C. M.; Roper, W. R.; Wight, L. J. J. Organomet. Chem. 1980, 199, C35−C38. (w) Caskey, S. R.; Stewart, M. H.; Kivela, J. E.; Sootsman, J. R.; Johnson, M. J. A.; Kampf, J. W. J. Am. Chem. Soc. 2005, 127, 16750− 16751. (x) Caskey, S. R.; Stewart, M. H.; Ahn, Y. J.; Johnson, M. J. A.; Rowsell, J. L. C.; Kampf, J. W. Organometallics 2007, 26, 1912−1923. (28) For reactions of S, Se, and I2 with W(IV) carbyne complexes at the WC bonds, see: (a) Gill, D. S.; Green, M.; Marsden, K.; Moore, I.; Orpen, G.; Stone, F. G. A.; Williams, I. D.; Woodward, P. J. Chem. Soc., Dalton Trans. 1984, 1343−1347. (b) Anderson, S.; Hill, A. F.; Nasir, B. A. Organometallics 1995, 14, 2987−2992. (c) Hill, A. F.; Malget, J. M. J. Chem. Soc., Dalton Trans. 1997, 2003−2004. Dovesi, S.; Solari, E.; Scopelliti, R.; Floriani, C. Angew. Chem., Int. Ed. 1999, 38, 2388−2391. (d) Cook, D. J.; Hill, A. F. Organometallics 2003, 22, 3502−3512. (29) Colebatch, A. L.; Hill, A. F.; Sharma, M. Organometallics 2015, 34, 2165−2182. (30) Galli, C.; Pau, T. Tetrahedron 1998, 54, 2893−2894. (31) Ben-Daniel, R.; de Visser, S. P.; Shaik, S.; Neumann, R. J. Am. Chem. Soc. 2003, 125, 12116−12117. (32) Swain, C. G.; Crist, D. R. J. Am. Chem. Soc. 1972, 94, 3195− 3200. (33) Wen, T. B.; Hung, W. Y.; Zhou, Z. Y.; Lo, M. F.; Williams, I. D.; Jia, G. Eur. J. Inorg. Chem. 2004, 2004, 2837−2846. (34) Sheldrick, G. M. Acta Crystallogr., Sect. A: Found. Crystallogr. 2008, A64, 112−122. (35) Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. J. J. Appl. Crystallogr. 2009, 42, 339−341. (36) (a) Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623−11627. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 5648−5652. (c) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Chem. Phys. Lett. 1989, 157, 200−206. (d) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter Mater. Phys. 1988, 37, 785−789. (e) Becke, A. D. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38, 3098− 3100. (37) Huzinaga, S.; Andzelm, J.; Klobukowski, M. R. A.; ESakai, Y.; Tatewaki, H. Gaussian Basis Sets for Molecular Calculations; Elsevier, 1984. (38) (a) Wadt, W. R.; Hays, P. J. J. Chem. Phys. 1985, 82, 284−298. (b) Hays, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299−310. (39) Hollwarth, A.; Bohme, M.; Dapprich, S.; Ehlers, A. W.; Gobbi, A.; Jonas, V.; Kohler, K. F.; Stegmann, R.; Veldkamp, A.; Frenking, G. Chem. Phys. Lett. 1993, 208, 237−240. (40) Benson, S. W. The Foundations of Chemical Kinetics; Krieger: Malabar, FL, 1982. (41) See for example: (a) Kang, X.; Luo, L.; Hu, S.; Luo, Y.; Hou, Z. J. Am. Chem. Soc. 2016, 138, 11550−11559. (b) Kojima, C.; Lee, K.H.; Lin, Z.; Yamashita, M. J. Am. Chem. Soc. 2016, 138, 6662−6669. (c) Bai, W.; Lee, K.-H.; Tse, S. K. S.; Chan, K. W.; Lin, Z.; Jia, G. Organometallics 2015, 34, 3686−3698. (d) Asakawa, H.; Lee, K.-H.; Lin, Z.; Yamashita, M. Nat. Commun. 2014, 5, 4245. (e) Ariafard, A.; Ghohe, N. M.; Abbasi, K. K.; Canty, A. J.; Yates, B. F. Inorg. Chem. 2013, 52, 707−717. (f) Schoenebeck, F.; Houk, K. N. J. Am. Chem. Soc. 2010, 132, 2496−2497. (g) Liu, Q.; Lan, Y.; Liu, J.; Li, G.; Wu, Y.D.; Lei, A. J. Am. Chem. Soc. 2009, 131, 10201−10210. (42) 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 E.01; Gaussian, Inc.: Wallingford, CT, 2004.
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DOI: 10.1021/acs.organomet.6b00860 Organometallics XXXX, XXX, XXX−XXX
