Preparation and reactivity of penta- and tetracoordinate platinum(ii) hydride complexes with P(OEt)3 and PPh(OEt)2 phosphite ligands†
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]](https://www.rsc.org/images/entities/char_e001.gif)
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.
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