Preparation and reactivity of penta- and tetracoordinate platinum(ii) hydride complexes with P(OEt)3 and PPh(OEt)2 phosphite ligands?

Dalton Transactions Pub Date: 2005-06-21 DOI: 10.1039/B505453B

Abstract

The pentacoordinate [PtH{P(OEt)3}4]BF4 (1) hydride complex was prepared by allowing the tetrakis(phosphite) Pt{P(OEt)3}4 to react with HBF4·Et2O at ?80 °C. Depending on the nature of the acid used, however, the protonation of the related Pt{PPh(OEt)2}4 complex yielded the pentacoordinate [PtH{PPh(OEt)2}4]BF4 (3) or the tetracoordinate [PtH{PPh(OEt)2}3]Y (4) [Y = BF4? (a), CF3SO3? (b), Cl? (c)] derivatives. Neutral PtHClP2 (7, 8) [P = P(OEt)3, PPh(OEt)2] hydride complexes were prepared by allowing PtCl2P2 to react with NaBH4 in CH3CN. The tetrakis(phosphite) [Pt{P(OEt)3}4](BF4)2 (2) derivative was also synthesised and then characterised spectroscopically and by an X-ray crystal structure determination. Reactivity with aryldiazonium cations of all the hydrides was investigated and found to proceed only with the PtHClP2 complex to yield the aryldiazene [PtCl(ArN[double bond, length as m-dash]NH)P2]BF4 [P = PPh(OEt)2] derivative. The hydrazine [PtCl(NH2NH2){PPh(OEt)2}2]BPh4 complex was also prepared by allowing PtHClP2 to react first with AgCF3SO3 and then with hydrazine.

Graphical abstract: Preparation and reactivity of penta- and tetracoordinate platinum(ii) hydride complexes with P(OEt)3 and PPh(OEt)2 phosphite ligands
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