| Co-Investigator(Kenkyū-buntansha) |
UEDA Tatsuo University of Osaka Prefecrure, College of Integrated Arts and Sciences, Departm, 総合科学部, 助手 (90151795)
ADACHI Tomohiro University of Osaka Prefecrure, College of Integrated Arts and Sciences, Departm, 総合科学部, 助手 (20079057)
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| Research Abstract |
Treatment of trans-M (CO) _2 (syn-Me_8 [16] aneS_4) (M=Mo, W) with excess MeOTf gave the tertiary sulfonium ion complex trans- {M (CO) _2 (syn-Me_9 [16] aneS_4)} OTf (1a, M=Mo ; =1b, M=W), while the similar reaction with HOTf (1 eq.) afforded the secondary sulfonium complex trans-M (CO) (OTf) (syrMe_8H [16] aneS_4) (2a, M=Mo ; 2b, M=W). The facile evolution of CO observed on protonation and the X-ray structural study of 1a indicate that Ppi-acceptor ability increases in the order, R_2SH^+>R_2MeS^+>R_2S.Oxidative addition of HOTf to 2 took place stepwisely to give 7-and 8-coordinate hydrido complexes trans-{WH (CO) (OTf) (syn-Me_8H [16] aneS_4)} OTf (3) and trans- {MH_2 (CO) (OTf) (syn-Me_8H [16] aneS_4)} (OTf) _2 (4a, M=Mo ; 4b, M=W), respectively. The X-ray structural study of 4b indicate that the W atom assumes distorted bicapped Oh with a novel W・・・H-S^+interaction (W・・・H1.92*). A similar protonation of 1 with HOTf produced trans- {MH (CO) (syn-Me_9 [16] aneS_4)} OTf (5a, M=Mo ; 5b, M=W). In 5a the hydrido ligand interacts strongly with the teriary sulfonium S atom to form Mo-H-S^+3c-2e bond(Mo-H1.48, H-S^+1.32*). The methylation of fac-M (CO) _3 (syn-Me_8 [16] aneS_4) (M=Mo, W) with an excess of MeOTf give fac {M (CO) _3 (syn-Me_9 [16] aneS_4)} OTf (6a, M=Mo ; 6b, M=W), where the teriary sulfonium ion is uncoordinated. In sharp contrast to the facile protonation of the thiamacrocycle in M (0) complexes, the Mo (IV) complexes trans-Mo (S) _2 (syn-Me_8 [16] aneS_4) and trans-Mo (N) (N_3) (syn-Me_8 [16] aneS_4) failed to give the corresponding secondary sulfonium ion complexes. Instead, they produced a novel dinuclear trisulfide {Mo_2 (mu-S) (S) _2 (syn-Me_8 [16] aneS_4) _2} (BF_4) _2 (7) containing a linear S=Mo-S-Mo=S linkage and parent imido complex trans- {Mo (NH) (OTf) (syn-Me_8[16]aneS_4)} OTf (8), respectively.
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