Axial ligand replacement reactions in tetrakis(.mu.-phosphato)diplatinum(III) complexes: coordination of amine, thioether and thiolate functionalities

Abstract

The labile water molecules in the diplatinum(III) complex 2(µ-04 )4( 20)21 2" are sequentially replaced by halide, amine, thioether, and thiolato ligands. The products can be identified by chromophore shifts in the intense da -» da* transitions. These binuclear complexes Pt2(u-P04H)4L22" and 2(µ-04 )4 24" (L = uncharged ligand, X = anionic ligand) show a pseudoquintet (1:8:18:8:1) pattern in the 31P NMR spectrum. The X-ray structure of (Ph4As)2[Pt2(M-P04H)4(S(CH2)4)2]'2H3P04 shows the crystals to be triclinic with space group Pi and Z = 1. The unit cell dimensions are as follows: a = 10.584 (1) Á; b = 11.373(1) A; c = 15.138 (2) A; a = 77.23 (1)°; ß = 70.72 (1)°; 7 = 75.23 (1)°; V= 1644.4 (4) A3. The Pt-Pt distance is 2.525 (1) A, and the Pt-S distances are 2.462 (1) A. All the nonlinear angles about platinum are close to 90°.

The hydrogenphosphate complex of (1,5-cyclooctadiene)iridium(I), {[Bu4N][(1,5-COD)Ir·HPO4]}n: synthesis, spectroscopic characterization, and ES-MS of a new, preferred precursor to HPO42− and Bu4N+ stabilized Ir(0)n nanoclusters

“…The significance of 1 is several fold: (i) Phosphateorganometallic complexes are little known even though inorganic metal-phosphate complexes are well precedented [2][3][4][5][6][7][8][9][10][11]; hence, 1 is of fundamental interest to organometallic chemistry. (ii) Phosphate is an O-donor ligand and, therefore, is part of a larger literature of O-donor organometallic complexes of, for example, ligands such as P 2 3 , C(Ph 2 PO) À 3 , R 3 SiO À , or simple RO À (see elsewhere for an extensive list of lead references to these and other O-donor ligands [12]).…”

Diplatinum(III) Complexes with Four Bridging 1-Methylcytosinato Nucleobases Derived from a Mononucleartrans-(NH3)2PtIIComplex and CuII

“…Diplatinum(III) complexes containing a metal−metal single bond exist in several variations, with four or two bridging ligands or even unsupported by any bridge. − Without exception, the orientation of the ligands about the Pt atom in two-fold-bridged compounds is cis ( head , tail or head , head if the ligands are unsymmetrical). In fact, complexes derived from cis -(NH 3 ) 2 Pt II or enPt II have contributed much to the development of the chemistry of diplatinum(III) species. − As to examples for four-fold-bridged diplatinum(III) compounds, both simple anions such as sulfate, , acetate, hydrogen phosphate, , pyrophosphite, acetamidate, , or substituted formamidinate 14 and S-containing heterocyclic pyrimidine , or pyridine ligands have been applied. Here we report on diplatinum(III) complexes containing four bridging 1-methylcytosinato anions which display the shortest Pt−Pt bonds hitherto observed among diplatinum(III) nucleobase complexes.…”

Oxidizing Elemental Platinum with Oleum under Harsh Conditions: The Unique Tris(disulfato)platinate(IV) [Pt(S2O7)3]2− Anion

“…Such dumbbells coordinated by chelating ligands are well established in platinum chemistry. [2][3][4][5][6][7][8][9][10][11][12] In subsequent investigations, we have pre-pared various sulfates displaying this structural feature, for example, K 4 [Pt 2 (SO 4 ) 5 ], [13] K 3 [Pt 2 (SO 4 ) 4 H(HSO 4 ) 2 ], [14] Gd 2 [Pt 2 (SO 4 ) 4 -(HSO 4 ) 2 ](HSO 4 ) 2 , [15] and the oxo-cluster-type compounds A 4 [Pt 12 O 8 (SO 4 ) 12 ] (A= NH 4 , K, Cs). [16,17] However, in none of our experiments we have ever observed an oxidation of the metal to its tetravalent state.…”