A series of (diazoalkane)rhodium(I) compounds of the general composition trans-[RhCl(N2CRR‘)(PiPr3)2] with R = R‘ = Ph, p-C6H4Me, p-C6H4Cl and R = Ph, R‘ = p-C6H4Me, o-C6H4Me, CH3, CH2Ph, CF3 has been prepared from the dimer [RhCl(PiPr3)2]2 (1) and the diazoalkane. This preparative route has also been extended to complexes in which the N2C unit(s) of 1,4-C6H4C(Ph)N2}2, 9-diazofluorene, 9,10-anthraquinone-9-diazide
一般组成的一系列(重氮烷)铑(I)化合物反式-[RhCl(N 2 CRR')(P i Pr 3)2 ],R = R'= Ph,p -C 6 H 4 Me,p -C 6 H 4 Cl和R = Ph,R'= p -C 6 H 4 Me,o -C 6 H 4 Me,CH 3,CH 2 Ph,CF 3由二聚体[RhCl(P i Pr 3)2 ]2(1)和重氮烷。该制备途径也已扩展到其中1,4-C 6 H 4 C(Ph)N 2 } 2的N 2 C单元,9-重氮芴,9,10-蒽醌-9-的配合物。二叠氮化物和3-甲基-1,4-萘醌-1-二叠氮与14电子[RhCl(P i Pr 3)2 ]片段连接。C(CO 2 Et)2 N 2的行为与预期相同,用1处理后即可得到复杂的反式-[RhCl N 2 C(CO 2 Et)2 }(Pi Pr 3)2),CH(CO 2 Et)N 2与相同的原料反应,生成二氮衍生物反式-[RhCl(N
Success and serendipity during studies aimed at preparing carbenerhodium(I) complexes
作者:Helmut Werner
DOI:10.1016/0022-328x(95)00529-y
日期:1995.9
The preparation of a series of new square-planar and half-sandwich type carbenerhodium(I) complexes will be described. The key to success is the use of the bis(stibane)rhodium compound trans-[RhCl(C2H4)(SbiPr3)2] as starting material from which in a stepwise manner the complexes trans-[RhCl(=CRR′)(SbiPr3)2] (L = PiPr3, AsiPr3, SbEt3) and [C5H5Rh(=CCR′)L] (L = SbiPr3, PiPr3, PMe3, CO, CNtBu) have been
将描述一系列新的正方形平面和半三明治型碳鎓(I)配合物的制备。成功的关键是使用双(二b)铑化合物反式-[RhCl(C 2 H 4)(Sb i Pr 3)2 ]作为起始原料,从该化合物逐步地以反式-[RhCl(= CRR')(Sb i Pr 3)2 ](L = P i Pr 3,As i Pr 3,SbEt 3)和[C 5 H 5 Rh(= CCR')L](L = Sb i Pr如图3所示,已经获得了P i Pr 3,PMe 3,CO,CN t Bu)。反式-[RhCl(= CPH 2)L 2 ] L = Sb i Pr 3,P i Pr 3或[C 5 H 5 Rh(= CPh 2)(P i Pr 3)]中卡宾配体的位移为CO或CN t Bu导致形成相应的羰基或异氰基铑化合物,并且CC耦合产物Ph 2 C = C = O和Ph 2 C = C = N t卜分别。卡宾配体还参与在反式-[RhCl(=
Dehydrative Cyclization of Alkynals: Vinylidene Complexes with the Cβ Incorporated into Unsaturated Five- or Six-Membered Rings
作者:María Batuecas、Luz Escalante、Miguel A. Esteruelas、Cristina García-Yebra、Enrique Oñate、Carlos Saá
DOI:10.1002/anie.201102969
日期:2011.10.4
A nice ring: The title compounds are easily prepared by dehydrativecyclization of terminal alkynals in the presence of osmium, iridium, and rhodium precursors (see scheme).
Metallorganische chemie in fester phase: Umlagerungs-, eliminierungs-und additionsreaktionen von organometallverbindungen ohne solvens
作者:Helmut Werner、Thomas Rappert、Matthias Baum、Arthur Stark
DOI:10.1016/0022-328x(93)86085-v
日期:1993.10
Several examples of organometallic reactions in the solid state are described. These include the synthesis of the vinylidenerhodium(I) complexes trans-[RhCl(CCHCHCH2)(PiPr3)2] (3) and trans-[RhCl(CCHSiR3)(PiPr3) 2] (8, 9) via rearrangement of the corresponding alkyne- or alkynyl(hydrido)metal isomers, the preparation of trans-[RhCl( CCHC(CH3)CH2)(PiPr3)2](5) by NH3 elimination from 4, the synthesis
The syntheses of the novel cyclopentadienylphosphinevinylidenerhodium complexes C5H5Rh(CCHR)(PPri3) (R = Ph, Me, H) and, for R = Ph, of the isomeric alkynyl hydrido compound C5H5 RhH(C2Ph)(PPri3) are reported. The square-planar complexes trans-[RhCl(RC2H)(PPri3)2] (IIa, IIb), which in solution are in equi-librium with the five-coordinated pyridine to give the octahedral compounds RhHCl(C2R)(PRri3)2(py)
新型环戊二烯膦膦乙烯基内酯络合物C 5 H 5 Rh(CCHR)(PPr i 3)(R = Ph,Me,H)的合成,以及对于R = Ph,是炔基氢化物的异构体C 5 H 5 RhH报告了(C 2 Ph)(PPr i 3)。方形平面络合物反式-[RhCl(RC 2 H)(PPr i 3)2 ](IIa,IIb),在溶液中与五配位吡啶处于平衡态,得到八面体化合物RhHCl(C 2) R)(PRr i 3)2(py)(VIa,VIb)。用NaC 5 H 5处理Via,VIb可获得高收率的亚乙烯基配合物IVa,IVb。Ç 5 ħ 5的Rh(CCH 2)(PPR我3)(IVc)中是直接从所获得的反式- [的RhCl(C 2 H ^ 2)(PPR我3)2 ](IIC)和NAC 5 ħ 5。机理研究证实,VIa,VIb与环戊二烯阴离子的反应主要是通过消除HCl产生的铑(I)化合物反式-[Rh(C