Chemistry of di- and tri-metal complexes with bridging carbene or carbyne ligands. Part 3. Synthesis of bimetallic platinum–tungsten complexes with µ-tolylidyne groups; crystal structure of [PtW(µ-C·C6H4Me-p)(CO)2(PMe2Ph)2(η-C5H5)]
- 1 January 1980
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 9,p. 1609-1614
- https://doi.org/10.1039/dt9800001609
Abstract
The tungsten–carbyne complex [W(C·C6H4Me-p)(CO)2(η-C5H5)] reacts with the compounds [Pt(C2H4)(PR3)2](PR3= PMe2Ph or PMe3) to give the dimetal species [PtW(µ-C·C6H4Me-p)(CO)2(PR3)2(η-C5H5)]. A related complex [PtWBr(µ-C·C6H4Me-p)(CO)4(PMe3)2] is produced quantitatively from [W(C·C6H4Me-p)(Br)(CO)4] and [Pt(C2H4)(PMe3)2]. In order to establish the molecular structure of this class of complex a single-crystal X-ray diffraction study was made on [PtW(µ-C·C6H4Me-p)(CO)2(PMe2Ph)2(η-C5H5)], crystals of which are monoclinic, space group P21/c, Z= 4, in a unit cell with lattice parameters a= 12.212(11), b= 9.339(6), c= 26.125(24)Å, and β= 92.77(7)°. The structure has been refined to R 0.031 (R′ 0.029) for 3 803 reflections measured at 200 K for 2.9 ⩽ 2θ⩽ 55°(Mo-KαX-radiation). In the molecule a Pt–W bond [2.751(1)Å] is bridged by a C·C6H4Me-p Group forming a ‘dimetallacyclopropene’ ring with Pt–C 1.997(9)Å and W–C 1.967(6)Å. The least-squares plane defined by the carbon atoms of the C·C6H4Me-p ligand is at 88.1° to the plane [graphic omitted]. The 1H, 31P, and 13C n.m.r. spectra of the compounds are discussed in relation to their structures.Keywords
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