000130302 001__ 130302
000130302 005__ 20240124152850.0
000130302 0248_ $$2sideral$$a61797
000130302 037__ $$aART-2007-61797
000130302 041__ $$aeng
000130302 100__ $$0(orcid)0000-0003-0341-7699$$aCasas, J. M.$$uUniversidad de Zaragoza
000130302 245__ $$aNew Mono- and Polynuclear Alkynyl Complexes Containing Phenylacetylide as Terminal Or Bridging Ligand. X-Ray Structures of the Compounds NBu 4[Pt(CH2C6H4P(o-Tolyl) 2-kC,P)(C=CPh)2], [Pt(CH2C 6H4P(o-Tolyl)2-kC,P)(C=CPh)(CO)], [{Pt(CH2C6H4P(o-..
000130302 260__ $$c2007
000130302 5203_ $$aThis work describes the synthesis of the compounds Q[Pt(CP)(CCPh)2] (Q = Li+ (1), NBu4+ (2). CP = CH2C6H4P(o-tolyl)2-κC,P) and their use as precursors for the preparation of homo- and heteropolynuclear complexes by reactions with Lewis acid species of transition metals, M (M = Cu(I), Ag(I), Tl(I), Pd(II), Pt(II)). These reactions give rise to heteropolynuclear complexes that exhibit different bonding patterns for the bridging alkynyl ligands, depending on M. The reaction of 2 with readily available M+ (M = Cu, Ag) species affords the discrete tetranuclear clusters [{Pt(CP)(CCPh)2M}2] (M = Cu (3), Ag (4)). The X-ray structure of 3 shows that in this complex both “Pt(CP)(CCPh)2” fragments are connected by two d10 metal centers and are stabilized by alkynyl bridging ligands, showing the stronger preference of the MI centers (MI = Cu, Ag) for the electron-rich alkynyl units than for the basic Pt(II) center. However, the reaction of 2 with TlPF6 rendered the tentatively tetranuclear complex [{Pt(CP)(CCPh)2Tl}2] (5), containing Pt→Tl dative bonds, which shows the higher affinity of thallium for the electron density of platinum(II) than for the alkynyl units. Moreover, the reaction of (NBu4)[Pt(CP)(CCPh)2] (2) with the neutral complex [Pd(C6F5)2(THF)2] yields the compound (NBu4)[Pt(CP)(CCPh)2Pd(C6F5)2] (11), in which the two alkynyl ligands are η2-bonded to Pd(II) in such a way that the “cis-Pt(CCPh)2“ fragment acts as a chelate ligand toward Pd(II). Meanwhile the reactions with the cationic and neutral Pt(II) complexes [Pt(CP)(THF)2]+ and [Pt(C6F5)2(THF)2] produce the complexes [{Pt(CP)(μ-CCPh)}2] (6) and (NBu4)[Pt(CP)(μ-CCPh)2Pt(C6F5)2] (12), both containing the double μ2-η2(σ,π)-alkynyl bridging system “Pt2(μ-CCPh)2” as a consequence of an alkynylating process. This bridging system “Pt2(μ-CCPh)2” can be broken by neutral ligands, L, to give mono(σ-alkynyl) complexes of Pt(II). Thus, the complexes [Pt(CP)(CCPh)L] (L = CO (7), py (8), tht (9), PPh3 (10)) have been obtained by reaction of 6 with L in a 1:2 molar ratio. When L = PPh3, the substitution reaction takes place with stereoretention, but not when L = CO, py, tht, as was conclusively established by an X-ray study on the complex [Pt(CH2C6H4P(o-tolyl)2)(CCPh)(CO)] (7). The cis or trans disposition of the two σ-C-donor ligands (C(CP), σ-CCPh) around the Pt center in complexes 6−10 and 12 seems to depend as much on the transphobia of pairs of trans ligands (T) as on the steric requirements of those in the cis configuration.
000130302 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000130302 590__ $$a3.833$$b2007
000130302 591__ $$aCHEMISTRY, ORGANIC$$b10 / 56 = 0.179$$c2007$$dQ1$$eT1
000130302 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b6 / 43 = 0.14$$c2007$$dQ1$$eT1
000130302 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000130302 700__ $$0(orcid)0000-0003-1374-5880$$aFornies,J.$$uUniversidad de Zaragoza
000130302 700__ $$0(orcid)0000-0003-1812-3175$$aFuertes,S.$$uUniversidad de Zaragoza
000130302 700__ $$0(orcid)0000-0002-4808-574X$$aMartin,A.
000130302 700__ $$0(orcid)0000-0002-0257-0483$$aSicilia,V.$$uUniversidad de Zaragoza
000130302 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000130302 773__ $$g26, 7 (2007), 1674-1685$$pOrganometallics$$tOrganometallics$$x0276-7333
000130302 8564_ $$s384632$$uhttps://zaguan.unizar.es/record/130302/files/texto_completo.pdf$$yVersión publicada
000130302 8564_ $$s3096312$$uhttps://zaguan.unizar.es/record/130302/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000130302 909CO $$ooai:zaguan.unizar.es:130302$$particulos$$pdriver
000130302 951__ $$a2024-01-24-15:01:12
000130302 980__ $$aARTICLE