Syntheses, Structures, and Reactions of 2-N-Acylamido-N,O Hydrido Complexes of Molybdenum(II) and Tung
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- 作者：Makoto Minato ; Hiroyuki Sakai ; Zu-Gan Weng ; Da-Yang Zhou ; Susumu Kurishima ; Takashi Ito ; Mikio Yamasaki ; Motoo Shiro ; Masako Tanaka ; and Kohtaro Osakada
- 刊名：Organometallics
- 出版年：1996
- 出版时间：October 29, 1996
- 年：1996
- 卷：15
- 期：22
- 页码：4863 - 4871
- 全文大小：391K
- 年卷期：v.15,no.22(October 29, 1996)
- ISSN：1520-6041
文摘
The N-acylamido complexes[MH{N(R1)COR2-N,O}(dppe)2](M = Mo, W; R1/R2 = Me/Me,Ph/Me, Me/H, Ph/H, (CH2)3, Ph/Ph; dppe =Ph2PCH2CH2PPh2)were synthesized byphotochemical or thermal reactions of[MoH4(dppe)2] ortrans-[W(N2)2(dppe)2]with N-alkylamides R1NHCOR2. An X-ray studyof[MoH{N(CH3)COCH3-N,O}(dppe)2]revealed adistorted-pentagonal-bipyramidal configuration with two phosphorusatoms, the nitrogenand the oxygen atoms of the amide, and a hydride lying in theequatorial plane. Thesecomplexes reacted with methanol or ethanol in toluene at ambienttemperature to give thenovel alkoxo hydrido complexes[MH2(OR)2(dppe)2] (R= Me, Et). The reactions apparentlyproceeded via a coordinatively unsaturated 16e intermediate, which isformed upon releaseof the N-acylamido ligand. The reactions between theamido complexes and catechols yieldedthe chelated catecholato complexes[MH2(catecholato-O,O')(dppe)2](catecholato =O2C6H4,O2C6H3(4-Me),O2C6H3(4-But),O2C6H3(4-COOEt), andO2C10H6). The structures ofcatecholatocomplexes, determined by single-crystal X-ray diffraction studies,exhibit distorted-dodecahedral geometry.