Pt 0 and Pd 0 Olefin Complexes of the Metalloid N‐Heterocyclic Carbene Analogues [E I (ddp)] (ddp=2‐{(2,6‐diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐pentene; E=Al, Ga): Ligand Substitution, HH and SiH Bond Activation, and Cluster Formation

Various products of the reaction of [E(ddp)] (ddp=2‐{(2,6‐diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐pentene; E=Al, Ga) with Pt 0 and Pd 0 olefin complexes are reported. Thus, the reaction of [Pt(cod) 2 ] (cod=1,5‐cyclooctadiene) with two equivalents of [Ga(ddp)] yields [Pt(1,3‐cod){Ga(ddp)} 2 ] ( 1 ), whereas treatment of [Pd 2 (dvds) 3 ] (dvds=1,1,3,3‐tetramethyl1,3‐divinyldisiloxane) with [E(ddp)] leads to the monomeric compounds [(dvds)Pd{E(ddp)}] (E=Ga ( 2 a ), Al ( 2 b )) by substitution of the bridging dvds ligand. Both 1 and 2 a readily react with strong π‐acceptor ligands such as CO or t BuNC to give the dimeric compounds [M{μ 2 ‐Ga(ddp)}(L)] (L=CO, t BuNC; M=Pt ( 3 a , 5 a ), Pd ( 3 b , 5 b )), respectively. Based on 1 H NMR spectroscopic data, [Pt{Ga(ddp)} 2 (CO)] is likely to be an intermediate in the formation of 3 a . Furthermore, reactions of 1 with H 2 and HSiEt 3 yield the monomeric compounds [Pt{Ga(ddp)} 2 (H) 2 ] ( 7 ) and [Pt{Ga(ddp)} 2 (H)(SiEt 3 )] ( 8 ). Finally, the reaction of [Pt(cod) 2 ] with one equivalent of [Ga(ddp)] in the presence of H 2 in hexane gives the new dimeric cluster [Pt{μ 2 ‐Ga(ddp)}(H) 2 ] 2 ( 9 ).