85422-05-5Relevant academic research and scientific papers
Dinuclear, metal-metal-bonded platinum(III) compounds. 2. Synthesis and properties of complexes containing the [Pt2(HPO4)4(B)2]2- anions (B = a heterocyclic tertiary amine) or the [Pt2(H2PO4)(HPO4) 3(py)2]- ion
Conder, Harold L.,Cotton, F. Albert,Falvello, Larry R.,Han, Scott,Walton, Richard A.
, p. 1887 - 1891 (2008/10/08)
The reactions of phosphoric acid solutions containing the diplatinum(III) anion [Pt2(HPO4)4]2- with heterocyclic tertiary amines afford yellow complexes of stoichiometry (BH)2[Pt2(HPO4)4(B)2], where B = pyridine, 4-methylpyridine, or 3,4-dimethylpyridine. These products are probably contaminated with small amounts of the mixed salts (BH)[Pt2(H2P-O4)(HPO4) 3(B)2]·H2O, a complex of this type apparently being the principal product when 4-phenylpyridine is used as the nitrogen base. During attempts to grow suitable crystals of the pyridine (py)-containing complex (pyH)2[Pt2(HPO4)4(py)2], we instead isolated (pyH)[Pt2(H2PO4)(HPO4) 3(py)2]·H2O, the identity of which was determined by an X-ray structure analysis. The crystals are orthorhombic, and the structure was solved and refined in space group Pc21n (a nonstandard setting of Pna21). The unit cell dimensions are as follows: a = 8.460 (2) A?; b = 16.476 (6) A?; c = 19.466 (6) A?; V = 2713 (2) A?3; Z = 4. The structure was refined to R = 0.031 and Rw = 0.039. The Pt-Pt distance is 2.494 (1) A?, the mean Pt-O(coord) distance is 2.004 [4] A?, and the mean P-O(coord) distance is 1.528 [4] A?. The Pt-N distances are 2.11 (2) and 2.18 (1) A?, with the py planes being almost perpendicular to each other and staggered with respect to the Pt-O bonds. The water molecule is loosely hydrogen bonded to the [Pt2(H2PO4)(HPO4) 3(py)2] ion. The pattern of P-O distances, the occurrence of hydrogen-bonded O?O contacts, and the chemical analysis are all consistent with the formulation of this compound. Preliminary studies of the reaction of (pyH)2[Pt2(HPO4)4(py)2] with triphenylphosphine and tert-butyl isocyanide have been carried out. Mononuclear products such as Pt(PPh3)2(O2CCH3)2 (formed in glacial acetic acid) and Pt(CN-t-Bu)2(CN)2 attest to the relative ease with which reductive cleavage of the Pt-Pt bond occurs.
