Synthesis of selenophosphinic and tellurophosphinic amides and amidato complexes. Crystal structures of Bu<sup>t</sup><sub>2</sub>P(Te)NH(C<sub>6</sub>H<sub>11</sub>), [Ti(η-C<sub>5</sub>H<sub>5</sub>)Cl<sub>2</sub>{Bu<sup>t</sup><sub>2</sub>P(Se)NPr<sup>i</sup>}] and [TiCl<sub>2</sub>{Bu<sup>t</sup><sub>2</sub>P(Se)N(C<sub>6</sub>H<sub>11</sub>)}<sub>2</sub>]·C<sub>7</sub>H<sub>8</sub>
作者:Manfred Bochmann、Gabriel C. Bwembya、Nicola Whilton、Xuejing Song、Michael B. Hursthouse、Simon J. Coles、Alexander Karaulov
DOI:10.1039/dt9950001887
日期:——
The reaction of Bu(2)(t)PNHR' with selenium or tellurium affords the chalcogenophosphinic amides Bu(2)(t)P(E)NHR' (E = Se or Te; R' = Pr-i or cyclo-C6H11). The compounds [Bu(2)(t)P(E)NHCH2](2) were prepared similarly. The crystal structure of Bu(2)(t)P(Te)NH(C6H11) was determined; it shows a short P-Te bond of 2.371(1) Angstrom and a rather long P-N bond of 1.781(4) Angstrom. The lithium salts Li[Bu(2)(t)P(Se)NR'] react with [TiCl3(cp)] (cp = eta-C5H5) to give [TiCl2(cp)Bu(2)(t)P(Se)NR'}]. The reaction of Li[Bu(2)(t)P(Se)NPri] with [TiCl4(thf)(2)] (thf = tetrahydrofuran) affords [TiCl3Bu(2)(t)P(Se)NPri)]. while a similar reaction with Li[Bu(2)(t)P(Se)N(C6H11)] leads to the isolation of [TiCl2Bu(2)(t)P(Se)N(C6H11}(2)]. The structures of [TiCl2(cp)Bu(2)(t)P(Se)NPri}] and [TiCl2Bu(2)(t)P(Se)N(C6H11)}(2)]. C7H8 have been determined by X-ray crystallography. The selenophosphinic amidato ligands are bidentate in ail cases. The former complex adopts a distorted square-pyramidal geometry with apical cp, while the latter is octahedral with cis-CI ligands and trans stereochemistry for the nitrogen donors.
KUCHEN, W.;LANGSCH, D.;PETERS, W., PHOSPH., SULFUR AND SILICON AND RELAT. ELEM., 54,(1990) N-4, C. 55-61