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• 548459-30-9 [Rh(Cp*)Cl₂(diphenyl-perfluorooctanoylphosphine)] 

Relevant academic research and scientific papers

Heteronuclear and heterovalent diphenylphosphido-bridged complexes of rhodium, iridium and ruthenium. Crystal structure of *1/2Et2O (COD = 1,5-cyclooctadiene)

Mononucelar complexes of formulae , BF4 and BF4 (M = Rh, Ir; L = C5Me5.M = Ru; L = p-Cymene; R = Ph, H; R' = H; Hacac = acetylacetone, but not in all possible combinations) have been prepared from the corresponding 2(μ-Cl)2> or and HPRR'.Complexes react with 2 (M' = Rh; diolefin = tetrafluorobenzobarrelene (TFB), 1,5-cyclooctadiene (COD).M' = Ir; diolefin = COD) to yield diphenylphoshido-bridged complexes of formula .The structure of *1/2Et2O has been determined by X-ray diffraction methods.The complex consists of two moieties, (C5Me5)RhCl and Rh(COD), doubly-bridged by a diphenylphosphido group and a chlorine atom.The two rhodium atoms are separated by 3.3657(6) Angstroem.

SYNTHESE UND REACTIVITAET VON 2: ADDITIONS- UND INSERTIONSREAKTIONEN VON SAUERSTOFF UND SEINEN HOMOLOGEN AN DIE Rh2P2-EINHEIT

2 (I) has been prepared from 2 via C5Me5Rh(PMe2H)Cl2 (II) as intermediate.Complex I reacts with oxygen and its congeners En (E = O, S, Se, Te) to form three different types of products (VII-XI) which originate from

Synthesis and transition metal chemistry of 'phosphomide' ligands: A comparison of the reactivity and electronic properties of diphenyl-P-perfluoro-octanoyl-phosphine, P-acetyl-dyphenylphophine and P-anisoyl-diphenylphosphine. X-ray crystal structure of [RhCp*(Ph2PC(O)CH3)Cl2]

A convenient synthesis of several 'phosphomide' ligands (P adjacent to carbonyl group) from secondary phosphines is reported. The new anisoyl substituted phosphines are considerable more stable to hydrolysis, and are stronger σ-donor ligands than P-acetyldiphenylphosphine as determined by the measurement of ν(CO) for the corresponding rhodium carbonyl complexes trans - [RhL2(CO)Cl]. In contrast, a new phosphomide derived from perfluoro-octanoyl chloride was found to be a highly unstable, electron poor π-acceptor ligand. The crystal structure of [RhCp*Cl2{Ph2PC(O)CH3}] showed a normal pseudo-octahedral pianostool molecular geometry with a Rh-P bond length of 2.3186(5) A?. The extra stability observed for the P-anisoyl phosphomides has led us to apply this class of ligand in rhodium catalysed hydroformylation for the first time.

Dinuclear homo- and heterometallic rhodium complexes containing PMe2 and PPh2 groups as bridging ligands. The crystal and molecular structure of [(C5Me5Rh)2(μ-PMe2)(μ-PPh 2)]

The reaction of [C5Me5Rh(PMe2H)Cl2] (4), which is prepared from [C5Me5RhCl2]2 (2) and PMe2H, with excess diethylamine, produces a mixture of [C5Me5(Cl)Rh(μ-PMe2)]2 (6), [C5Me5Rh(PMe2NEt2)Cl2] (7), and [C5Me5Rh(μ-PMe2)]2 (9). 7 reacts with HF (in pyridine) and with HCl (in benzene) to form the complexes [C5Me5Rh(PMe2F)Cl2] (8) and [C5Me5Rh(PMe2Cl)Cl2] (10), respectively, the latter of which is reduced with sodium amalgam to give 9. Compound 9 is also obtained by reduction of 6 with Na-Hg. Treatment of [C5Me5Rh(PPh2H)Cl2] (11) with excess NEt2H leads to the formation of [C5Me5Rh(μ-PPh2)]2 (13) and [(C5Me5Rh)2(μ-PPh2)(μ-Cl)] (14). The structurally related complexes [(C5Me5Rh)2(μ-PMe2)(μ-PPh 2)] (15) and [(C5Me5Rh)2(μ-PPh2)(μ-SMe)] (16) have been prepared from 14 by bridge-ligand exchange. The crystal and molecular structure of 15 have been determined. For C34H46P2Rh2 (15): triclinic, P1; a = 10.053 (3), b = 11.271 (4), c = 16.761 (4) A?; α = 93.32 (2)°, β= 85.78 (2)°, γ = 116.45 (2)°; V = 1694.8 (6) A?3; Z = 4; for 4938 observed reflections, RF = 3.39%. 15 contains a folded butterfly Rh2P2 core with a 111.5 (2)° core dihedral angle and a Rh-Rh bond of 2.7952 (4) A?. The synthesis of the dinuclear homo- and heterometallic complexes [C5Me5Rh(μ-PMe2)2MC 5H5] (17, M = Rh; 18, M = Co) and [C5Me5Rh(μ-PMe2)2RuC 6H6] (19) has been achieved starting from [C5Me5Rh(PMe2H)2], CH3Li, and [C5H5M(CO)I2] or [C6H6RuCl2]2, respectively.