ABSTRACT
The reduction of [CoLBr2], a CoII complex supported by a diisopropylphosphinoquinoline (L) ligand, induced a ligand coupling giving access to a (PNNP) supported CoII complex which was isolated in 70% yield. This complex was formed using a minimum of 2 equivalents of a reductant (either Mn or KC8). The fate of [CoLBr2] in the presence of 1 equivalent of a reductant was more difficult to study; nevertheless, a CoI complex was characterised in the solid state. In order to determine whether this ligand coupling could occur with other 3d metals, L supported FeII and NiII complexes were synthesised. While no compound could be identified upon reduction of [FeLBr2], both [NiLBr2] and [NiL2Br](Br) led to the reduction at the metal center allowing the isolation of an original Ni0 trimer in a satisfactory yield. This study shows the different behaviours of these 3d metal complexes in the presence of a reductant.
ABSTRACT
P,N phosphinoquinoline based ligands differing by the nature of the phosphorus substituent (i Pr, Ph) were employed to synthesize a series of cobalt(II) complexes ([LCoBr2 ], [L2 CoBr](PF6 ) and [L'2 CoBr](PF6 )). The latter were obtained in high yield and characterized among others by X-ray analysis and elemental analysis. Complex [L2 CoBr](PF6 ) showed a very good catalytic activity for the hydrosilylation of various ketones. The catalysis proceeds at a low catalytic loading (1â mol %) with only 1 equivalent of Ph2 SiH2 in mild conditions and was efficient with aliphatic or aromatic ketones giving moderate to excellent yields of the corresponding silylated ether.
ABSTRACT
A novel heterobimetallic tantalum/iridium hydrido complex, [{Ta(CH2tBu)3}{IrH2(Cp*)}] 1, featuring a very short metal-metal bond, has been isolated through an original alkane elimination route from Ta(CHtBu)(CH2tBu)3 and Cp*IrH4. This molecular precursor has been used to synthesize well-defined silica-supported low-coordinate heterobimetallic hydrido species [≡SiOTa(CH2tBu)2{IrH2(Cp*)}], 5, and [≡SiOTa(CH2tBu)H{IrH2(Cp*)}], 6, using a surface organometallic chemistry (SOMC) approach. The SOMC methodology prevents undesired dimerization as encountered in solution and leading to a tetranuclear species [{Ta(CH2tBu)2}(Cp*IrH)]2, 4. This approach therefore allows access to unique low-coordinate species not attainable in solution. These original supported Ta/Ir species exhibit drastically enhanced catalytic performances in H/D exchange reactions with respect to (i) monometallic analogues as well as (ii) homogeneous systems. In particular, material 6 promotes the H/D exchange between fluorobenzene and C6D6 or D2 as deuterium sources with excellent productivity (TON up to 1422; TOF up to 23.3 h-1) under mild conditions (25 °C, sub-atmospheric D2 pressure) without any additives.
ABSTRACT
The straightforward synthesis of a new unsymmetrical hydroxy-tethered N-heterocyclic carbene (NHC) ligand, HL, is presented. The free ligand exhibits an unusual OH-carbene hydrogen-bonding interaction. This OH-carbene motif was used to yield 1)â the first tantalum complex displaying both a Fischer- and Schrock-type carbene ligand and 2)â a unique NHC-based early/late heterobimetallic complex. More specifically, the protonolysis chemistry between the ligand's hydroxy group and imido-alkyl or alkylidene-alkyl tantalum precursor complexes yielded the rare monometallic tantalum-NHC complexes [Ta(XtBu)(L)(CH2 tBu)2 ] (X=N, CH), in which the alkoxy-carbene ligand acts as a chelate. In contrast, HL only binds to rhodium through the NHC unit in [Rh(HL)(cod)Cl] (cod=cycloocta-1,5-diene), the hydroxy pendant arm remaining unbound. This bifunctional ligand scaffold successfully promoted the assembly of rhodium/tantalum heterobimetallic complexes upon either 1)â the insertion of [Rh(cod)Cl]2 into the Ta-NHC bond in [Ta(NtBu)(L)(CH2 tBu)2 ] or 2)â protonolysis between the free hydroxy group in [Rh(HL)(cod)Cl] and one alkyl group in [Ta(NtBu)(CH2 tBu)3 ].
