|
|||||
|
|
Reactions of the haloalcohols HO(CH2)nCl (n = 2, 3) with platinum(II) - alkynyl and -alkyne complexes. X-ray crystal structure of trans-[Pt(Me) {C(OCH2CH2Cl) (CH2Ph)} (PPh3)2] [BF4] |
|
| Authors: | Umberto Belluco Roberta Bertani Rino A Michelin Mirto Mozzon Franco Benetollo Gabriella Bombieri and Robert J Angelici |
| Institution: | a Istituto di Chimica Industriale and Centro di Studio per la Chimica e Tecnologia dei Composti Metallorganici degli Elementi di Transizione del CNR, Facoltà di Ingegneria, Università di Padova, Via F. Marzolo 9, 35131, Padua, Italy b Istituto di Chimica e Tecnologie Inorganiche dei Materiali Avanzati del CNR, Corso Stati Uniti 4, 35100, Padua, Italy c Istituto di Chimica Farmaceutica, Università di Milano, Viale Duca degli Abbruzzi, 20131, Milan, Italy d Department of Chemistry, Iowa State University, Ames, IA 50011, USA |
| Abstract: | The chloro complexes trans-Pt(Me)(Cl)(PPh3)2], after treatment with AgBF4, react with 1-alkynes HC---C---R in the presence of NEt3 to afford the corresponding acetylide derivatives trans-Pt(Me) (C---C---R) (PPh3)2] (R = p-tolyl (1), Ph (2), C(CH3)3 (3)). These complexes, with the exception of the t-butylacetylide complex, react with the chloroalcohols HO(CH2)nCl (n = 2, 3) in the presence of 1 equiv. of HBF4 to afford the alkyl(chloroalkoxy)carbene complexes trans-Pt(Me) {CO(CH2)nCl](CH2R) } (PPh3)2]BF4] (R = p-tolyl, N = 2 (4), N = 3 (5); R=Ph, N = 2 (6)). A similar reaction of the bis(acetylide) complex trans-Pt(C---C---Ph)2(PMe2Ph)2] with 2 equiv. HBF4 and 3-chloro-1-propanol affords trans-Pt(C---CPh) {C(OCH2CH2CH2Cl)(CH2Ph) } (PMe2Ph)2]BF4] (7). T alkyl(chloroalkoxy)-carbene complex trans-Pt(Me) {C(OCH2CH2Cl)(CH2Ph) } (PPh3)2]BF4] (8) is formed by reaction of trans-Pt(Me)(Cl)(PPh3)2], after treatment with AgBF4 in HOCH2CH2Cl, with phenylacetylene in the presence of 1 equiv. of n-BuLi. The reaction of the dimer Pt(Cl)(μ-Cl)(PMe2Ph)]2 with p-tolylacetylene and 3-chloro-1-propanol yields cis-PtCl2{C(OCH2CH2CH2Cl)(CH2C6H4-p-Me}(PMe2Ph)] (9). The X-ray molecular structure of (8) has been determined. It crystallizes in the orthorhombic system, space group Pna21, with a = 11.785(2), B = 29.418(4), C = 15.409(3) Å, V = 4889(1) Å3 and Z = 4. The carbene ligand is perpendicular to the Pt(II) coordination plane; the PtC(carbene) bond distance is 2.01(1) Å and the short C(carbene)-O bond distance of 1.30(1) Å suggests extensive electronic delocalization within the Pt---C(carbene)---O moietry. |
| Keywords: | Crystal structures Platinum complexes Alkynyl complexes Carbene complexes |
| 本文献已被 ScienceDirect 等数据库收录！ | |