Amide ligand

Organic Reactions Catalyzed by Metal Complexes Bearing Phosphinous Amide Ligands... 

Following the general trend of this account, monodentate phosphinous amide ligands and bidentate AT-phosphino phosphinous amides or bis(amino-phosphanes) are included in the following discussion, but not other bidentate ligands bearing additional, different phosphorus functionalities, as for instance phosphinous amide-phosphane bidentate ligands. 

The catalytic hydroformylation of alkenes has been extensively studied. The selective formation of linear versus branched aldehydes is of capital relevance, and this selectivity is influenced by many factors such as the configuration of the ligands in the metallic catalysts, i.e., its bite angle, flexibility, and electronic properties [152,153]. A series of phosphinous amide ligands have been developed for influencing the direction of approach of the substrate to the active catalyst and, therefore, on the selectivity of the reaction. The use of Rh(I) catalysts bearing the ligands in Scheme 34, that is the phosphinous amides 37 (R ... 

Figure 2.13 Selected examples of gold(lll) complexes containing chelating bis(amidate) ligands.

Kilpin, K.J., Henderson, W. and Nicholson, B.K. (2007) Organogold(III) complexes containing chelating bis (amidate) ligands Synthesis, characterisation and biological activity. Polyhedron, 26, 434. 

Scheme 10.81 Y-catalysed hydroaminations of 2-amino-5-hexene with bis(thiopho-sphonic amidates) ligands.

Scheme 10.82 Y-catalysed hydroamination of 1-amino-2,2-dimethyl-4-pentene with bis(thiophosphonic amidates) ligand.

The crystal structure of a CODH/ACS enzyme was reported only in 2002.43,44 It reveals a trio of Fe, Ni, and Cu at the active site (6). The Cu is linked to the Ni atom through two cysteine-S, the Ni being square planar with two terminal amide ligands. Planarity and amide coordination bear some resemblance to the Ni porphinoid in MCR. A two-metal ion mechanism is likely for acetyl CoA synthesis, in which a Ni-bound methyl group attacks an adjacent Cu—CO fragment with formation of a Cu-acyl intermediate. A methylnickel species in CODH/ACS has been identified by resonance Raman spectroscopy.45... 

Comba et al. reported structural properties (in the solid state and in solution) and molecular modeling studies on a dicopper(II) complex (545) (SP) of a macrocyclic amide ligand.443 In 1993... 

Dianionic bis(amide) ligands bearing additional donor atoms have been described by several researchers. High activities for ethylene polymerization are observed for pyridyldiamido zirconium complexes such as (42) (1,500gmmol-1 bar-1 h-1),145 although the corresponding titanium complex is much less active.146... 

The use of chiral amide ligands has been restricted to rhodium, where the catalyst precursor is [Rh(BH4)(amide)py2Cl2]. The work has been reviewed (10, 35) cinnamate derivatives were reduced to up to 57% ee, and hydrogenation of a carbon- nitrogen double bond in folic acid leads to tetrahydrofolic acid with high biological activity (308). 

Pell and Armor found entirely different products in alkaline solution. Above pH 8.3, the sole ruthenium product of the reaction of Ru(NH3)g+ with NO was the dinitrogen complex Ru(NH3)5(N2)2+. Under these conditions the rate law proved to be first-order in [Ru(NH3)g+], [NO] and [OH-]. A likely mechanism is the reversible reaction of Ru(NH3)3+ with OH- to give the intermediate Ru(NH3)5(NH2)2+, followed by electrophilic NO attack at the amide ligand and release of water. However, the kinetic evidence does not exclude other sequences. 

Pritchett et al.119 found that Ti(OPr )4 did not react with the bis(sulfon-amide) ligand itself, so they postulated that a chiral ligand initially reacted with the diethylzinc and was subsequently transferred to the titanium in the next step. Based on this assumption, they presented an improved procedure for the asymmetric alkylation of aldehyde to overcome the poor solubility of the li-... 

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