Investigations of LiP(SiMe2CH2SiMe3)-PtBu2, the Surprising Byproduct in the Metalation of (Me3Si)2P-PtBu2

被引：3

作者：

Sattler, Ewald ^{[1
]}

Szilvasi, Tibor ^{[2
]}

Matern, Eberhard ^{[1
]}

Bombicz, Petra ^{[3
]}

Gamer, Michael ^{[1
]}

Okrut, Alexander ^{[4
]}

Kovacs, Ilona ^{[5
]}

机构：

[1] Karlsruher Inst Technol, Inst Anorgan Chem, Engesserstr 15,Geb 30-45, D-76131 Karlsruhe, Germany

[2] Univ Wisconsin Madison, Dept Chem & Biol Engn, 1415 Engn Dr, Madison, WI 53706 USA

[3] Hungarian Acad Sci, Res Ctr Nat Sci, POB 17, H-1521 Budapest, Hungary

[4] Univ Calif Berkeley, Dept Chem & Biomol Engn, Berkeley, CA 94720 USA

[5] Budapest Univ Technol & Econ, Dept Inorgan & Analyt Chem, Szt Gellert Ter 4, H-1521 Budapest, Hungary

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2017年 / 46期

关键词：

Lithium; Diphosphanides; Donor ligands; NMR spectroscopy; Structure elucidation; Density functional calculations; DIPHOSPHANES R2P-P(SIME3)LI R; PHOSPHINOPHOSPHINIDENE (BU2P)-BU-T-P; CRYSTAL-STRUCTURE; COMPLEXES; PHOSPHANYLPHOSPHIDO; SILYLPHOSPHANES; BUTYLLITHIUM; DERIVATIVES; PHOSPHANES; CHEMISTRY;

D O I：

10.1002/ejic.201701077

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

During the metalation reaction of (Me3Si)(2)P-PtBu2 with nBuLi, a byproduct with the sum formula Li(thf)(n)P(SiMe2CH2SiMe3)-PtBu2 (2, n = 2.7-1) was detected. The formation of the unexpected substituent SiMe2CH2SiMe3 was investigated, a possible reaction mechanism based on DFT calculations established, and the compound synthesized following an independent route. Compound 2 eliminated thf in vacuo to yield the dimeric [Li(thf)P(SiMe2CH2SiMe3)-PtBu2](2) (2a). Exchange of thf with tmeda [Me2N(CH2)(2)NMe2] in 2 led to the solvent-separated ion pair [Li(tmeda)(2)](+)[(SiMe2CH2SiMe3)P-PtBu2](-) (4). The solid-state structures of 2a, 4, and the contact ion pair Li(thf)(tmeda)P(SiMe2CH2SiMe3)-PtBu2 (5) were determined by single-crystal X-ray diffraction analysis. Extensive variable-temperature multinuclear NMR studies were carried out to elucidate the structures of these compounds in solution and to compare them with the solid-state structures.

引用

页码：5521 / 5528

页数：8

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