A convenient synthesis of bis(tri-t-butylphosphine)platinum(0) and its oxidative addition and ligand exchange reactions

Abstract

Summary Pt[P(t-Bu)3]2 (I) is prepared in high yield from a facile reaction of P(t-Bu)3 with K2PtCl4. Its oxidative addition reactions with CHCl3, CH2Cl2, MeI, and I2, and substitution reactions with CO, M(CO)6 (M=Cr, Mo, W), and t-BuNC have been investigated. Reaction with CHCl3 affords trans-PtHCl[P(t-Bu)3]2 (II) and [ Pt ( µ − Cl ) { P ( t − Bu ) 2 CMe 2 C ︹ H 2 } ] 2 (III), and reaction with CH2Cl2 yields PtCl { P ( t − Bu ) 2 CMe 2 C ︹ H 2 } P(t-Bu) 3 (IV). Pt2Me2(μ-I)2[P(t-Bu)3]2 (VI) and P(t-Bu)3-MeI are formed in the reaction of I with MeI. VI undergoes intramolecular metalation to give [ Pt ( µ − I ) { P ( t − Bu ) 2 CMe 2 C ︹ H 2 } ] 2 (V), and CH4. Reaction of I with I2 results in the formation of V, trans-PtHI[P(t-Bu)3]2 (VII) and P(t-Bu)3I2. CO readily displaces one phosphine from I to give Pt3[P(t-Bu)3]3(CO)3 (VIII). I reacts with M(CO)6 to afford VIII and M(CO)5P(t-Bu)3. t-BuNC replaces both the phosphines from I to give Pt3(t-BuNC)3(μ-t-BuNC)3 (IX).