The synthesis and structural characterisation of [Pt3Au2(μ-Cl)(μ-SO2)2(PCy3)3(P{p-C6H4F}3)2](PF6): The first example of a trigonal-bipyramidal platinum-gold cluster compound

Heterobimetallic gold-platinum phosphine complexes. X-ray crystal and molecular structures of [(PPh3)Pt(AuPPh3)6](NO3)2 and [(PPh3)(CO)Pt(AuPPh3)6](PF6)2

“…The spectroscopic properties are identical for the three complexes of 3. 31P NMR (CH2C12, 25 (sextet with 195Pt satellites, Jmn.nc = 1330 Hz, 2Juc_P = 3.0 Hz, Vuc.P = 13.2 Hz). IR (KBr): v(CO) 1946 cm'1, v(13CO) 1900 cm"1 [i>-(CO)/v(13CO) = 1.024], The equivalent conductance of the Cl" salt (81.5 cm2 mhos mol"1) is indicative of a 1:1 electrolyte in CH3CN solution.…”

Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems

“…In both clusters,t he -AuPPh 3 fragments symmetrically bridge the three Pt centers affording aP t 3 Au tetrahedron (4)o raP t 3 Au 2 trigonal bipyramid (5). [45] These extra electrons also allow for the formation of 5 via addition of as econd equivalent of [AuPPh 3 ] + , at ransformation which is not accessible to [Pt 3 (m 3 -AuPCy 3 )-(m-CO) 3 (PCy 3 ) 3 ] + [46] and has not been reported for any phosphine-substituted Pt 3 (m-CO) 3 (PR 3 ) 3 cluster.Accordingly, these reactions leading to the formation of complexes 2-5 demonstrate that while e À equivalents are housed in the ligand-based p*m anifold of K 2 [1], electrophilic functionalization can proceed at the platinum centers of the triangulo-Pt 3 core. [45] These extra electrons also allow for the formation of 5 via addition of as econd equivalent of [AuPPh 3 ] + , at ransformation which is not accessible to [Pt 3 (m 3 -AuPCy 3 )-(m-CO) 3 (PCy 3 ) 3 ] + [46] and has not been reported for any phosphine-substituted Pt 3 (m-CO) 3 (PR 3 ) 3 cluster.Accordingly, these reactions leading to the formation of complexes 2-5 demonstrate that while e À equivalents are housed in the ligand-based p*m anifold of K 2 [1], electrophilic functionalization can proceed at the platinum centers of the triangulo-Pt 3 core.…”

“…While reminiscent of the formation of [Pt 3 (m 3 -AuPCy 3 )(m-CO) 3 (PCy 3 ) 3 ] + ,which is produced by capping the corresponding neutral Pt 3 cluster with a[ AuPCy 3 ] + fragment, [44] it should be noted that the two additional valence electrons possessed by K 2 [1]c ompared to Pt 3 (m-CO) 3 (PCy 3 ) 3 allows for the isolation of an anionic Pt/Auc luster,o fw hich only one other structurally characterized example is known. [45] These extra electrons also allow for the formation of 5 via addition of as econd equivalent of [AuPPh 3 ] + , at ransformation which is not accessible to [Pt 3 (m 3 -AuPCy 3 )-(m-CO) 3 (PCy 3 ) 3 ] + [46] and has not been reported for any phosphine-substituted Pt 3 (m-CO) 3 (PR 3 ) 3 cluster.Accordingly, these reactions leading to the formation of complexes 2-5 demonstrate that while e À equivalents are housed in the ligand-based p*m anifold of K 2 [1], electrophilic functionalization can proceed at the platinum centers of the triangulo-Pt 3 core.…”

Gold–Heterometal Interactions and Bonds

“…All pentanuclear Au-Pt clusters whose structure has been reported so far exhibit a trigonal bipyramidal skeleton with Au-phosphine units m 3 -bridging a Pt 3 triangle [546,547], as in [{(Me 3 P)Au} 2 Pt 3 (m-dppm) 3 ](PF 6 ) 2 400 [547], or an Au 4 Pt core with an equatorial Pt atom, as in [{(Ph 3 P)Au} 4 Pt(dppe)](PF 6 ) 2 401 [548]. Octahedral Au 2 Pt 3 (Pt 1Àx Ni x ) and Au 2 Pt 2 (Pt 2Ày Ni y ) cores, with substitutional Ni/Pt disorder (see Section 3.7.1) have also been described [491].…”