Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 106. Synthesis and reactions of the alkylidyne complexes [M(CR)(CO)2{(C6F5)AuC(pz)3}](M = WorMo, R = alkyloraryl, pz = pyrazol-1-yl); crystal structure of [WPtAU(C6F5)(µ3-CMe)(CO)2(PMe2Ph)2{(C6F5)AuC(pz)3}]
- 1 January 1990
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 12,p. 3701-3708
- https://doi.org/10.1039/dt9900003701
Abstract
Treatment of the salts [M (CR)(CO)2{HC(pz)3}][BF4][M = W or Mo, R = alkyl or aryl, HC(pz)3= tris(pyrazol-1 -yl)methane] in thf (tetrahydrofuran) with NaOEt, followed by [Au(C6F5)(tht)](tht = tetrahydrothiophene), affords the neutral alkylidynemetal compounds [M(CR)(CO)2{(C6F5)AuC(pz)3}](M = W or Mo, R = C6H4Me-4; M = W, R = Me or C6H3Me2-2,6). The complexes (M = W, R = Me or C6H4Me-4) have been used to prepare several compounds containing heteronuclear metal–metal bonds, including [WAuX(µ-CMe)(CO)2{(C6F5)AuC(pz)3}](X = Cl or C6F5), [WCo2(µ3-CR)(CO)8{(C6F5)AuC(pz)3}], [WPt(µ-CR)(CO)2(PMe2Ph)2{(C6F5)AuC(pz)3}], and [W2Pt(µ-CR)2(CO)4{(C6F5)AuC(pz)3}2]. The cluster compound [WPtAu(C6F5)(µ3-CMe)(CO)2(PMe2Ph)2{(C6F5)AuC(pz)3}] has been synthesised by different routes, and its structure established by X-ray diffraction. The core of the molecule consists of a WPtAu triangle [W–Pt 2.798(2), W–Au 2.841(2), and Pt–Au 2.932(2)Å] asymmetrically capped by an ethylidyne group [µ-C–W 2.06(3), µ-C–Pt 2.05(3), and µ-C–Au 2.31 (3)Å]. The latter lies appreciably further from the Au atom than from the W or Pt atoms. The two carbonyl ligands semi-bridge the W–Pt [W–C–O 160(2)°] and W–Au [W–C–O 165(3)°] bonds. The Pt atom carries the PMe2Ph groups [P–Pt 2.26(1) and 2.32(1)Å], and the Au atom is co-ordinated by the C6F5 group [C–Au 2.04(3)Å]. The W atom is ligated by the three nitrogens of the (C6F5)AuC(pz)3 moiety (N–W average 2.21 Å). The n.m.r. data (1H, 13C-{1H}, 31P-{1H}, and 19F-{1H}) for the new compounds are reported and discussed where appropriate.Keywords
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