Formation of Novel P-Functionalized Ligands by Insertion Reactions of RNCX (R = Ph, X = O, S; R = Pri, X = O) into the Zr−P Bond of [Cp°2ZrCl(PHCy)] (Cp° = η5-C5EtMe4, Cy = Cyclohexyl) and [Cp‘2ZrCl{PH(TRIP)}] (Cp‘ = η5-C5MeH4, TRIP = 2,4,6-Pri3C6H2)
摘要:
[Cp degrees(2)ZrCl(PHCy)] (1; Cp degrees = eta(5)-C5EtMe4, Cy = cyclohexyl) and [Cp'2ZrCl{PH(TRIP)}] (2; Cp' = eta(5)-C5MeH4,TRIP = 2,4,6-(Pr3C6H2)-C-i) readily insert RNCX (R = Ph, X = S, O; R = Pr-i, X = O) to give [Cp degrees(2)ZrCl{eta(2)-XC(PHCy)NR}] (X = S, R = - Ph (3); X = O, R = Ph (4); X = O, R = Pr-i (5)) and [ Cp'2ZrCl{eta(2)-XC{PH(TRTP)}NR}] (X = S, R = Ph (6); X = O; R = Ph (7); X = O, R = Pr-i (8)). 3-8 were characterized spectroscopically (IR, NMR, MS), and crystal structure determinations on 4-6 showed an eta(2) bonding mode (X,N) of the XC(PHR')NR (R' = Cy, TRIP) ligands. Of the two possible coordination modes of the ligand, 4 and 5 are obtained exclusively as the endo isomer, in which the NR group is adjacent to the Zr-Cl bond, while for 6-8, both isomers (endo and exo) are formed (1:8 (6), 1:30 (7) and 1:5 (8)), whereby the exo isomer is favored. The exo isomer of 6 was structurally characterized.
Modular solid-phase synthesis, catalytic application and efficient recycling of supported phosphine–phosphite ligand libraries
作者:Frank J. L. Heutz、Paul C. J. Kamer
DOI:10.1039/c5dt03226a
日期:——
A highly modular solid-phase synthetic approach is presented which provides facile access to libraries of recyclable phosphine–phosphite ligands in quantitative yield requiring only minimal work-up.
C5Me5) with LiPHR (1:1 or 1:2) gives the phosphinidene-bridged tantalum(IV) complexes trans-[Cp*TaCl(μ-PR)}2] [R = Cy (1), tBu (2), Ph (3), 2,4,6-Me3C6H2 (Mes) (4b)]. When the reaction with LiPHMes is carried out in a 1:1 ratio, cis-[Cp*TaCl(μ-PMes)}2] (4a) is also formed besides 4b. For comparison, cis-[Cp′TaCl(μ-PMes)}2] (5) was prepared from [Cp′TaCl4] (Cp′ = C5MeH4) and LiPHMes (1:1). 1−5 are diamagnetic
Phosphide coupling in the reaction of Sn(NMe2)2 with MesPHLi; synthesis and structure of the Sn(ii) phosphide dianion [{Sn(μ-PMes)}2(MesP)2]2− (Mes = 2,4,6-Me3C6H2)
作者:Andrew D. Bond、Alexander Rothenberger、Anthony D. Woods、Dominic S. Wright
DOI:10.1039/b010201f
日期:——
In contrast to the reactions of other primary phosphides with
Sn(NMe2)2, the reaction of MesPHLi with
Sn(NMe2)2 results in partial coupling of MesP groups
in the product (which contains the novel Sn(II) dianion
[(Sn(μ-PMes)}2-
(MesP)2]2â).
Fragmentation of an imido tin(II) cubane; syntheses and structures of heterobimetallic complexes containing tin(II) imido and phosphinidine anions
作者:Robert E. Allan、Michael A. Beswick、Natalie L. Cromhout、Michael A. Paver、Paul R. Raithby、Alexander Steiner、Mark Trevithick、Dominic S. Wright
DOI:10.1039/cc9960001501
日期:——
The reactions of the imido tin(II) cubane [SnNBut]4 with 3 equiv. of [C10H7NHLi](C10H7= 1-naphthyl) and 6 equiv. of [C6H11PHLi](C6H11= cyclohexyl) produce [LI(thf)4]+[(ButN)(C10H7N)3Sn3Li·thf]–·thf·PhMe 1 and [Sn2(PC6H11)3}2Li4·4thf]·2thf 2, respectively, containing the first structurally characterized polyimido and polyphosphinidine anions of a divalent group 14 metal.
Terminal phosphinidene formation via tantalaziridine complexes
作者:Matthew A. Rankin、Christopher C. Cummins
DOI:10.1039/c2dt31082a
日期:——
Terminal, 4-coordinate phosphinidenes of Ta supported by bulky anilide ligands are prepared by an apparent reaction sequence involving metallaziridine phosphanide complexes.