Reactivity of Group 10 halides toward (Ph2PN=)C(Ph)[N(SiMe3)2], (NC5H4){(Ph2PN=)C[N(SiMe3) 2]}-4 and C6H4{C(=NPPh2)[N(SiMe3) 2]}2-1,4

Abstract

Interaction of [NiBr2(dme)] (dme = 1,2-dimethoxyethane) with 1 equivalent of (Ph2PN=)C(Ph)[N(SiMe3)2] L1 in tetrahydrofuran gave cis-[NiBr2{(Ph2PNH)C(Ph)(=NH)}] 1, metathesis of this compound with excess NH4BF4 in methanol gave cis-[Ni{(Ph2PNH)C(Ph)(=NH)}2][BF4]2 2. Reaction of [NiBr2(dme)] with 1 equivalent of (NC5H4){Ph2PN=)C[N(SiMe3) 2]}-4 L3 followed by metathesis with excess NH4BF4 in methanol gave cis-[Ni{(NC5H4)[(Ph2PNH)C(=NH)]-4} 2[BF4]2 3. Reaction of [PdCl2(PhCN)2] with 1 equivalent of L1 in acetonitrile gave cis-[PdCl2{(Ph2PNH)C(Ph)(=NH)}] 4, and with 0.5 equivalent of C6H4{C(=NPPh2)[N(SiMe3) 2]}2-1,4 L2 in tetrahydrofuran gave cis-[(PdCl2)2{C6H4[C(=NPPh 2){N(SiMe3)2}]2-1,4}] 5 and cis-[(PdCl2)2{C6H4[C(NHPPh 2)-(=NH)]2-1,4}] 6. Interaction of [PdCl2(PhCN)2] with L3 in 1:1 and 3:2 molar ratios gave cis-[PdCl2{(NC5H4)-[(Ph 2PNH)C(=NH)]-4}] 7 and trans-[PdCl2{cis-PdCl2[(NC5H 4){(Ph2PNH)C(=NH)}-4]}2] 8, respectively. Reaction of [MCl2(PhCN)2] (M = Pd or Pt) with 2 equivalents of L3 followed by metathesis with excess NH4BF4 in methanol gave cis-[M{(NC5H4)[(Ph2PNH)C(=NH)]-4}{(NC 5H4)[(Ph2PNH)C(=N)]-4}][BF4] (Pd 9 or Pt 10). Crystal structures of compounds 1, 4, 7, 8, 9 and 10 have been determined.