TY - JOUR
T1 - The clusters [Ma(ECp*)b] (M = Pd, Pt; e = Al, Ga, In)
T2 - Structures, fluxionality, and ligand exchange reactions
AU - Steinke, Tobias
AU - Gemel, Christian
AU - Winter, Manuela
AU - Fischer, Roland A.
PY - 2005/2/18
Y1 - 2005/2/18
N2 - The synthesis and structural characterization of the novel homoleptic cluster complexes [Pd2(GaCp*)2(μ2- GaCp*)3] (1c), [Pd3(GaCp*)4(μ 2-GaCp*)4] (2b) and [Pd3(AlCp*) 2(μ2-AlCp*)2(μ3-AlCp *)2] (3) (Cp* = C5Me5) are presented. Furthermore, ligand exchange reactions of these cluster complexes are explored. In contrast to the electronically and sterically saturated complexes [M(ECp*)4] (M = Ni, Pd, Pt), the new unsaturated analogues [Ma(ER)b] (E = Al, Ga, In) react with a variety of typical ligands (Cp*Al, CO, phosphines, isonitriles) to give new di-and tri-substituted compounds like [Pt2(GaCp*)2(μ 2-AlCp*)3] (1d), [PdPt-(GaCp*)(PPh 3)(μ2,-GaCp*)3] (4b), or [Pd 3(PPh3)3(μ2-InCp*) (μ3-InCp*)2] (8). The trends of the reactivity of [Ma(ER)b] as well as their fluxional behavior in solution has been elucidated by NMR spectroscopy, resulting in a mechanistic rationale for the ligand exchange reactions as well as the fluxional processes.
AB - The synthesis and structural characterization of the novel homoleptic cluster complexes [Pd2(GaCp*)2(μ2- GaCp*)3] (1c), [Pd3(GaCp*)4(μ 2-GaCp*)4] (2b) and [Pd3(AlCp*) 2(μ2-AlCp*)2(μ3-AlCp *)2] (3) (Cp* = C5Me5) are presented. Furthermore, ligand exchange reactions of these cluster complexes are explored. In contrast to the electronically and sterically saturated complexes [M(ECp*)4] (M = Ni, Pd, Pt), the new unsaturated analogues [Ma(ER)b] (E = Al, Ga, In) react with a variety of typical ligands (Cp*Al, CO, phosphines, isonitriles) to give new di-and tri-substituted compounds like [Pt2(GaCp*)2(μ 2-AlCp*)3] (1d), [PdPt-(GaCp*)(PPh 3)(μ2,-GaCp*)3] (4b), or [Pd 3(PPh3)3(μ2-InCp*) (μ3-InCp*)2] (8). The trends of the reactivity of [Ma(ER)b] as well as their fluxional behavior in solution has been elucidated by NMR spectroscopy, resulting in a mechanistic rationale for the ligand exchange reactions as well as the fluxional processes.
KW - Carbenoids
KW - Cluster compounds
KW - Fluxionality
KW - Group 13 elements
KW - Transition metals
UR - http://www.scopus.com/inward/record.url?scp=14844290282&partnerID=8YFLogxK
U2 - 10.1002/chem.200400959
DO - 10.1002/chem.200400959
M3 - Article
AN - SCOPUS:14844290282
SN - 0947-6539
VL - 11
SP - 1636
EP - 1646
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 5
ER -