185249-76-7Relevant academic research and scientific papers
Benzynechromium tricarbonyl. Further synthetic studies
Cullen, William R.,Rettig, Steven J.,Zhang, Hongli
, p. 53 - 64 (1996)
The thermolysis of Ru3(CO)11[Ph2PC6H 5Cr(CO)3] affords two isomers of the benzyne derivative Ru3(CO)7(C6H4) [PPhC6H5Cr(CO)3]2 ((5) and (6)). The crystal structure of 5, previously determined, shows the phenyl groups are trans to the Ru3-triangle; in 6 they are probably cis and on the same side of the Ru3-triangle as the benzyne moiety. Os3(CO)11[Ph2PC6H 5Cr(CO)3] decomposes on heating to afford a benzyne derivative of a less common class Os3(CO)9(C6H4)[PC6H 5Cr(CO)3] (7), and an electron deficient molecule Os3(CO)8(PhPC6H4)[Ph 2PC6H5Cr(CO)3] (8), in which the PhPC6H4 moiety acts as a four-electron donor. The isopropylphosphine derivatives M3(CO)11[Pri2PC6H 5Cr(CO)3] (M=Ru, Os), also undergo thermolysis to afford HRu3(CO)8[C6H4Cr(CO) 3](PPri2) (10), Ru(CO)3[Pri2PC6H 5Cr(CO)3]2 (11), H2Os3(CO)8[PriPC6H 4Cr(CO)3] (12) and H2Os3(CO)8[PriPC6H 4Cr(CO)3] [Pri2PC6H5-Cr(CO)3] (13). Complex 10 is probably a benzynechromium tricarbonyl derivative with a Cr-Ru bond. The phosphines are trans in complex 11, a derivative of Ru(CO)5. The structures of complexes 12 and 13 are closely related and the orthometalated [PC6H4Cr(CO)3] moiety is acting as a four-electron donor to the cluster. Crystal data: for 8 (C41H24CrO11Os3P 2·CH2Cl2): monoclinic, a = 13.039(3), b = 18.001(2), c = 20.125(2) A?, β = 108.42(1)°, Z=4, space group P21/n; for 11 (C33H38Cr2O9P2Ru): monoclinic, a = 15.390(1), b = 10.241(2), c = 23.490(1) A?, β = 96.686(6)°, Z=4, space group P21/a; for 12 (C21H13CrO12Os3P): orthorhombic, a = 14.695(2), b = 16.696(2), c = 11.186(1) A?, Z = 4, space group P212121; for 13 (C35H32Cr2O14Os3P 2·2CH2Cl2): monoclinic, a = 11.536(2), b = 18.354(4), c = 23.176(3) A?, β = 98.43(2)°, Z = 4, space group P21/n. The structures were solved by Patterson methods and were refined by full-matrix least-squares procedures to R = 0.057, 0.031, 0.030 and 0.032 (Rw = 0.065, 0.030, 0.028 and 0.030) for 6320, 6103, 3529 and 6042 reflections with I ≥ 3σ (I), respectively.
