Transition‐Metal Complexes with Bidentate Ligands Spanning trans‐Positions. Part XVII. Some platinum(II) complexes with anionic ligands such as methoxide, formate, carboxylate, hydride, and borohydride, and the X‐ray crystal structure of [PtHCl()] (PP = 2,11‐bis(diphenylphosphinomethyl)benzo[c]phenanthrene)

Abstract

ChemInform Abstract trans-Complexes of the type PtMeX(P1-P1) such as (I) and (III) as well as PtHX(P1-P1) such as (IV) and (VI) are prepared. Their decompositions to the corresponding trans-hydride complexes (II) and (V), respectively, are studied. Some binuclear complexes are also obtained. Thus, the hydride-bridged one (IX) can be synthesized by reaction of the methanol analogue (VIII) with sodium format (VII) as shown. The hydridomethyl-bis(phosphine) complex (XII) is prepared via the γ-picoline analogue. The structure of the analogous diphosphine complex (XIII), substitution product from the bis(triphenylphosphine) analogue, is determined by X-ray analysis (space group P21/c, Z=4).

Trans-chelating diphosphines, the elusive ligands!

“…In fact the exhaustive studies performed by Venanzi and co-workers resulted in a series of 19 papers in Helvetica Chimica Acta related to the characterization and reactivity of its derivatives [5,[21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37]! Numerous complexes with different coordination numbers and geometries have been synthesized and the structure of many of them has been elucidated by means of X-ray diffraction ( Table 1).…”

“…By reaction of Pt(C 2 H 4 ) 3 with 1 some dinuclear species of formula (Pt(C 2 H 4 ) 2 ) 2 1 with the ligand bridging between two metals have been characterized [32]. In spite of the size of the chelate ring, there are even examples of Pt hydridobridged dimeric compounds with the ligand coordinating in a cis-manner to each metal center [35]! Analysis of the different X-ray structures of ligand 1 showed in all cases, the phenanthrene unit of the backbone significantly deviated from planarity due to steric interactions between the H(1) and H (12).…”

Organodiphosphines in Pt(II) coordination complexes

“…The values of the "bite" angles are 86. 111 The Pt-H bond distance is 1.50(9) Å, 110 and for the latter derivative, the value is not available.…”

“…8,[24][25][26][27][28][29][30][31][32][33][34][35][42][43][44][45][46][95][96][97][100][101][102][103][104][105][106]110,111 with one chelated P,P ligand plus another chelated ligand with donor sites: O+O,[35][36][37][38][39][40][41] N+N, 47,48 S+S,[89][90][91][92][93][94] Se+Se,98,99 O+N 107,108 and N+Se 109. These complexes crystallized in the four crystal classes: tetragonal (0.8%) < triclinic (17.7%) < orthorhombic (20.5%) < monoclinic (61%).…”

Studies of gas‐phase fragmentation reactions of [Pd(PPh3)2(OCOR)]+ by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

“…Recently, electrospray ionization (ESI)6 has provided many opportunities to analyze the coordination chemistry of metal complexes and organometallic systems 7, 8. Combined with tandem mass spectrometric (MS/MS) methods involving collision‐activated dissociation (CAD), this technique has been extensively used for structural characterization of metal compounds and mechanism deduction of some gas‐phase reactions 9–13. O'Hair and co‐workers have investigated the gas‐phase mechanism of platinum(II) complexes involving ligand loss and decarboxylation reactions by using ESI and MS/MS,8, 10–12 and Traeger used ESI to elucidate the structures of thiosalicylic metal complexes and study some other transition‐metal coordination complexes 14…”