铂辅助的羰基稳定的磷叶立德与五氟苯腈和乙腈加成反应，生成含亚氨基磷烷和/或N键合的β-亚氨基磷叶立德配体的铂（II）配合物。反式-[PtCl(2){E-NH=C(C(6)F(5))C(=PPh(3))C(O)Me}(2)]和反式-[PtCl(2){E-N(=PPh(3))C(C(6)F(5))=CHCO(2)Et}{E-NH=C(C(6)F(5))C(=PPh(3))CO(2)Et}]的晶体和分子结构。

Platinum-Assisted Addition of Carbonyl-Stabilized Phosphorus Ylides to Pentafluorobenzonitrile and Acetonitrile To Give Platinum(II) Complexes Containing Iminophosphorane and/or N-Bonded beta-Imino Phosphorus Ylide Ligands. Crystal and Molecular Structures of trans-[PtCl(2){E-NH=C(C(6)F(5))C(=PPh(3))C(O)Me}(2)] and trans-[PtCl(2){E-N(=PPh(3))C(C(6)F(5))=CHCO(2)Et}{E-NH=C(C(6)F(5))C(=PPh(3))CO(2)Et}].

作者信息

Vicente José, Chicote María Teresa, Beswick Michael A., Ramirez De Arellano M. Carmen

机构信息

University Chemical Laboratory, Lensfield Road, CB2 1EW Cambridge, U.K.

出版信息

Inorg Chem. 1996 Oct 23;35(22):6592-6598. doi: 10.1021/ic951666a.

DOI:10.1021/ic951666a

PMID:11666809

Abstract

PtCl(2) reacts with C(6)F(5)CN to give trans-[PtCl(2)(NCC(6)F(5))(2)] (1) which, in turn, reacts with carbonyl-stabilized phosphorus ylides Ph(3)P=CHR [R = C(O)Me, CO(2)Et] to give trans-[PtCl(2){NH=C(C(6)F(5))C(=PPh(3))CO(2)Et}{NCC(6)F(5)}] (2a), trans-[PtCl(2){NH=C(C(6)F(5))C(=PPh(3))CO(2)Et}(2)] (3a), trans-[PtCl(2){E-NH=C(C(6)F(5))C(=PPh(3))C(O)Me}(2)] (3b) or trans-[PtCl(2){E-N(=PPh(3))C(C(6)F(5))=CHCO(2)Et}{E-NH=C(C(6)F(5))C(=PPh(3))CO(2)Et}] (4), depending on the reaction conditions. Similarly, Ph(3)P=CHCO(2)Me reacts with trans-[PtCl(2)(NCMe)(2)] to give trans-[PtCl(2){NH=CMeC(=PPh(3))CO(2)Me}(NCMe)] (2b). Complex 3b.CH(2)Cl(2) crystallizes in the triclinic system, space group P&onemacr;, with a = 7.596(2) Å, b = 12.694(3) Å, c = 16.962(3) Å, alpha = 104.28(3) degrees, beta = 102.73(3) degrees, gamma = 104.43(3) degrees, V = 1464.2(6) Å(3), and Z = 1. The structure was refined to values of R1 = 0.0411 and wR2 = 0.1172 [I >2sigma(I)] and shows two chloro and two N-bonded beta-imino phosphorus ylide ligands in a trans geometry. Complex 4 crystallizes in the monoclinic system, space group P2(1)/c, with a = 16.400(8) Å, b = 14.354(7) Å, c = 23.221(12) Å, alpha = 90(3) degrees, beta = 92.42(2) degrees, gamma = 90 degrees, V = 5462(5) Å(3), and Z = 4. The structure was refined to values of R1 = 0.0246 and wR2 = 0.0557 [I >2sigma(I)]. This complex has also a trans-geometry and shows that while the attack of the ylide on one of the nitrile ligands produces a beta-imino-phosphorus ylide ligand the addition on the second nitrile leads to an iminophosphorane ligand.

摘要

二氯化铂（PtCl₂）与五氟苯甲腈（C₆F₅CN）反应生成反式 - [PtCl₂(NCC₆F₅)₂]（1），该产物又与羰基稳定的磷叶立德Ph₃P = CHR [R = C(O)Me，CO₂Et]反应，根据反应条件生成反式 - [PtCl₂{NH = C(C₆F₅)C(= PPh₃)CO₂Et}{NCC₆F₅}]（2a）、反式 - [PtCl₂{NH = C(C₆F₅)C(= PPh₃)CO₂Et}₂]（3a）、反式 - [PtCl₂{E - NH = C(C₆F₅)C(= PPh₃)C(O)Me}₂]（3b）或反式 - [PtCl₂{E - N(= PPh₃)C(C₆F₅)= CHCO₂Et}{E - NH = C(C₆F₅)C(= PPh₃)CO₂Et}]（4）。类似地，Ph₃P = CHCO₂Me与反式 - [PtCl₂(NCMe)₂]反应生成反式 - [PtCl₂{NH = CMeC(= PPh₃)CO₂Me}(NCMe)]（2b）。配合物3b·CH₂Cl₂在三斜晶系中结晶，空间群为P&onemacr;，a = 7.596(2) Å，b = 12.694(3) Å，c = 16.962(3) Å，α = 104.28(3)°，β = 102.73(3)°，γ = 104.43(3)°，V = 1464.2(6) Å³，Z = 1。结构精修后R₁ = 0.0411，wR₂ = 0.1172 [I >2σ(I)]，显示出反式几何构型中有两个氯和两个与氮键合的β - 亚氨基磷叶立德配体。配合物4在单斜晶系中结晶，空间群为P2(1)/c，a = 16.400(8) Å，b = 14.354(7) Å，c = 23.221(12) Å，α = 90(3)°，β = 92.42(2)°，γ = 90°，V = 5462(5) Å³，Z = 4。结构精修后R₁ = 0.0246，wR₂ = 0.0557 [I >2σ(I)]。该配合物也具有反式几何构型，表明虽然叶立德对其中一个腈配体的进攻产生了一个β - 亚氨基 - 磷叶立德配体，但对第二个腈的加成导致了一个亚氨基磷烷配体。