The First Examples of Isonitrile Insertion into a Phosphido Bridge and the Crystal and Molecular Structures of [Pt2(μ-PBut2){μ,η2-P(But2)C(NAr)}(CNAr)2] and [Pt{μ,η2-P(But2)C(NHAr)}(CNAr)]2(CF3SO3)2 (Ar = p-Tolyl)

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The platinum(I) dinuclear carbonyl [Pt 2 (μ-PBu t 2 ) 2 (PBu t 2 H)(CO)] ( 1 ) reacts with organic isonitriles RNC (R = p -tolyl, Bu t, PhCH 2 ), yielding the mono- and disubstituted derivatives [Pt 2 (μ-PBu t 2 ) 2 (PBu t 2 H)(CNR)] ( 2, R = p -tolyl; 3, R = Bu t; 4, R = PhCH 2 ) and [Pt(μ-PBu t 2 )(CNR)] 2 ( 5, R = p -tolyl; 6, R = Bu t; 7, R = PhCH 2 ). Only with the aromatic isonitrile does the reaction proceed through two further well-separated steps, giving [Pt 2 (μ-PBu t 2 ){μ,η 2 -P(Bu t 2 )C( NAr)}(CNAr) 2 ] ( 8 ) and [Pt{μ,η 2 -P(Bu t 2 )C( NAr)}(CNAr)] 2 ( 9 ). These arise from the unprecedented reversible isonitrile insertion into the M−P bonds of the phosphido-bridges. When 8 or 9 are reacted with CF 3 SO 3 H, the cyclic carbenes [Pt 2 (μ-PBu t 2 ){μ,η 2 -P(Bu t 2 )C(NHAr)}(CNAr) 2 ]CF 3 SO 3 ( 10 ) and [Pt{μ,η 2 -P(Bu t 2 )C(NHAr)}(CNAr)] 2 (CF 3 SO 3 ) 2 ( 11 ) are respectively formed. The crystal and molecular structures of complexes 8 and 11 were solved by X-ray diffraction.