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DOI: 10.1039/A607909A (Paper) J. Chem. Soc., Dalton Trans., 1997, 1295-1300

Platinum(II) phosphine complexes of dicarboxylates and ammonia: crystal structures of [{Pt(PPh3)2}2{µ -1,3-(O2C)2C6H4} 2], [{Pt(PPh3)2(NH3)}2 {µ-1,4-(O2C)2C6H4 }][PF6]2 and cis-[Pt(PPh3)2(NH3) 2][NO3]2

Andrew D. Burrows , D. Michael P. Mingos , Simon E. Lawrence , Andrew J. P. White and David J. Williams

Abstract

The reaction of [Pt(PPh3)2(CO3)] with a rigid dicarboxylic acid H2L gave rise to dimeric compounds [{Pt(PPh3)2}2(µ-L)2 ] 1 [H2L = C6H4(CO2 H)2-1,4 (terephthalic acid) a, C6H4(CO2H)2-1,3 (isophthalic acid) b, trans,trans-HO2CCH[double bond, length as m-dash]CHCH [double bond, length as m-dash]CHCO2H (muconic acid) c or 4,4′-HO2CC6H4C6H 4CO2H (biphenyldicarboxylic acid) d], which have been characterised spectroscopically and, in the case of 1b, crystallographically. When the reaction was carried out in the presence of NH4PF6 the NH4+ competed with the carboxylic acid and the major product from the reaction was [{Pt(PPh3)2(NH3)}2 (µ-L)][PF6]22, which has been characterised crystallographically for L = terephthalate. This suggests that NH4+ is acidic enough to react with [Pt(PPh3)2(CO3)], which has been confirmed by the synthesis of cis-[PtL2(NH3)2]X2 [L = PPh3, X = PF63a or NO33b; L = PEt3, X = PF64a or NO34b; L2 = Ph2PCH2CH2 PPh2 (dppe), X = PF65a] from [PtL2(CO3)]. The complex cis-[Pt(PPh3)2(15NH3 )2][NO3]2 was synthesized from 15NH4NO3 and characterised by a combination of 31P-{1H}, 15N-{1H}, 195Pt and 1H NMR spectroscopy. The crystal structure of cis-[Pt(PPh3)2(NH3)2 ][NO3]23b has been determined and shows strong hydrogen bonding between the co-ordinated ammonia and the nitrate counter ions. The compound PhC2CO2H also reacted with [PtL2(CO3)], though the products were not the expected bifunctional carboxylates cis-[PtL2(O2CC2Ph)2 ] but the bis(phenylalkynyl) compounds cis-[PtL2(C2Ph)2] (L = PPh36, L2 = dppe 7).

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