单和双核铑(I)和铑(III)与大块膦2,6-Me 2 C 6 H 3 CH 2 CH 2 P t Bu 2的配合物,包括第一个结构表征的顺式构型二羰基化合物,顺式- [RhCl(CO)2(PR 3)]
摘要:
从格氏试剂2,6-Me 2 C 6 H 3 CH 2 CH 2 MgCl逐步制备大块的官能化膦2,6-Me 2 C 6 H 3 CH 2 CH 2 P t Bu 2(3)。,t BuPCl 2和t BuLi。膦3与烯烃化合物[RhCl(C 2 H 4)2 ] 2和[RhCl(C 8 H 14)反应2 ] 2,得到取代产物[的RhCl(烯烃)(3)] 2(8,9),其中9(烯烃= C 2 H ^ 4)已被表征晶体。尽管9对3呈惰性,但它在氢气氛下与3反应,通过二聚体[RhH 2 Cl(3)] 2(10)生成二氢配合物[RhH 2 Cl(3)2 ](11)。)作为中介。在乙烯存在下,11转换为9。反应8(烯烃= C 8 ħ 14与鏻盐)3 ·HCl的得到一个的[RhHCl混合物2(3)] 2(12)和3,其在60升温℃下产生[RhHCl 2(3)2 ](13)。在Al 2 O 3上通过柱色谱法
An Unprecedented Dinuclear Alkylrhodium(III) Complex Built up by Two 14-Electron [RhCl2(alkyl)(PR3)] Units
摘要:
Reaction of HCl with [RhCl(C2H4)(PR3)]2 affords the dinuclear alkylrhodium(III) complex [RhCl2(C2H5)(PR3)]2, the structure of which has been determined crystallographically. PR3 is the formerly unknown trialkyl phosphine tBu2PCH2CH2C6H3-2,6-Me2, prepared in three steps from tBuPCl2. Treatment of the title compound with CO gives the mononuclear rhodium dicarbonyl cis-[RhCl(CO)2(PR3)], being the first fully characterized complex of this type.
Mono- and Dinuclear Rhodium(I) and Rhodium(III) Complexes with the Bulky Phosphine 2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub>CH<sub>2</sub>CH<sub>2</sub>P<i>t</i>Bu<sub>2</sub>, Including the First Structurally Characterized Cis-Configurated Dicarbonyl Compound, <i>cis</i>-[RhCl(CO)<sub>2</sub>(PR<sub>3</sub>)]
作者:Giuseppe Canepa、Carsten D. Brandt、Helmut Werner
DOI:10.1021/om034348p
日期:2004.3.1
[RhCl(C8H14)2]2 to give the substitution products [RhCl(olefin)(3)]2 (8, 9), of which 9 (olefin = C2H4) has been characterized crystallographically. While 9 is rather inert toward 3, it reacts with 3 under a hydrogen atmosphere to give the dihydrido complex [RhH2Cl(3)2] (11) via the dimer [RhH2Cl(3)]2 (10) as an intermediate. In the presence of ethene, 11 is reconverted to 9. The reaction of 8 (olefin = C8H14)
从格氏试剂2,6-Me 2 C 6 H 3 CH 2 CH 2 MgCl逐步制备大块的官能化膦2,6-Me 2 C 6 H 3 CH 2 CH 2 P t Bu 2(3)。,t BuPCl 2和t BuLi。膦3与烯烃化合物[RhCl(C 2 H 4)2 ] 2和[RhCl(C 8 H 14)反应2 ] 2,得到取代产物[的RhCl(烯烃)(3)] 2(8,9),其中9(烯烃= C 2 H ^ 4)已被表征晶体。尽管9对3呈惰性,但它在氢气氛下与3反应,通过二聚体[RhH 2 Cl(3)] 2(10)生成二氢配合物[RhH 2 Cl(3)2 ](11)。)作为中介。在乙烯存在下,11转换为9。反应8(烯烃= C 8 ħ 14与鏻盐)3 ·HCl的得到一个的[RhHCl混合物2(3)] 2(12)和3,其在60升温℃下产生[RhHCl 2(3)2 ](13)。在Al 2 O 3上通过柱色谱法
An Unprecedented Dinuclear Alkylrhodium(III) Complex Built up by Two 14-Electron [RhCl<sub>2</sub>(alkyl)(PR<sub>3</sub>)] Units
作者:Giuseppe Canepa、Carsten D. Brandt、Helmut Werner
DOI:10.1021/ja020560t
日期:2002.8.1
Reaction of HCl with [RhCl(C2H4)(PR3)]2 affords the dinuclear alkylrhodium(III) complex [RhCl2(C2H5)(PR3)]2, the structure of which has been determined crystallographically. PR3 is the formerly unknown trialkyl phosphine tBu2PCH2CH2C6H3-2,6-Me2, prepared in three steps from tBuPCl2. Treatment of the title compound with CO gives the mononuclear rhodium dicarbonyl cis-[RhCl(CO)2(PR3)], being the first fully characterized complex of this type.