585571-75-1

Upstream product

• 1079-66-9 chloro-diphenylphosphine 
• 199111-38-1 1-iodo-8-methylnaphthalene 
• 1162-90-9 1-naphthyl(diphenyl)phosphine 

Downstream Products

• 585571-65-9 [([8-(diphenylphosphanyl)naphth-1-yl]methyl-(C,P))tris(trimethylphosphane)cobalt(I)] 

Relevant academic research and scientific papers

C-H activation of diphenylphosphinoaryl-derivatives with dimethyltetrakis(trimethylphosphine)iron(II)

Fe(CH3)2(PMe3)4 reacts with 1-(diphenylphosphino)naphthalene or benzyldiphenylphosphine within 4 h at 20 °C to give the novel metallated methyl iron complexes Fe(CH3){P(C6H5)2(C10H6)}(PMe3)3 (1) and Fe(CH3){(C6H4)CH2P(C6H5)2}(PMe3)3 (3), respectively, via selective activation of the C-H bond of the pre-chelating ligands. The complexes are thermally unstable releasing metal through a reductive elimination of the aromatic backbone and leading to a C,C-coupling product that is regiospecifically methylated, namely 8-methyl(diphenylphosphino)naphthalene (2). Carbonylation (1 bar, 20 °C, 1 h) of complex 1 effects monosubstitution of a trimethylphosphine ligand trans to the metallated 8-C atom to afford Fe(CH3){P(C6H5)2(C10H6)}(CO)(PMe3)2 (4). The remaining methyl group in the parent complex 1 reacts with trimethylsilylethyne and tert-butylethyne affording the new complexes 5 and 6 bearing an alkynyl substituent trans to the diphenylphosphino anchoring group. The complexes 1 and 3-6 are diamagnetic and possess octahedral coordination geometry. All novel complexes were fully characterized by spectroscopic methods and by X-ray diffraction.

Five- and six-membered cobaltocycles with C,P-chelating ligands through regiospecific cyclometalation of mono(2-substituted) triphenylphosphane

Cyclometalation in the aliphatic ring occurs in the reaction between [CoCH3(PMe3)4] and 5-(diphenylphosphanyl)-1,2,3,4-tetrahydronaphthalene to give [{8-(diphenylphosphanyl)-1,2,3,4-tetrahydronaphthyl-(C1,P)} tris(trimethylphosphane)cobalt] (1), containing a five-membered metallacycle as shown in the molecular structure. While 1-(diphenylphosphanyl)naphthalene reacts accordingly, affording [{8-(diphenylphosphanyl)naphthyl-(C1,P)}tris(trimethylphos phane)cobalt] (2), 2-(diphenylphosphanyl)biphenyl yields ortho-metalated [{2-(diphenylphosphanyl)-3-phenylphenyl-(C1,P)}tris (trimethylphosphane)cobalt] (3), containing a four-membered metallacycle. 1-(Diphenylphosphanyl)-8-methylnaphthalene is metalated in the aliphatic substituent to form [{[8-(diphenylphosphanyl)naphth-1-yl]methyl-(C,P)}tris (trimethylphosphane)cobalt] (4). The molecular structure shows a trigonal-bipyramidal configuration of the cobalt atom accommodating a six-membered metallacycle. 2-(Diphenylphosphanyl)styrene replaces two trimethylphosphane ligands to give [{2-(diphenylphosphanyl)styrene-(C,C-η2,P)/methyl-bis (trimethylphosphane)cobalt] (5), avoiding metalation. Replacement of equatorial trimethylphosphane in compounds 1-3 by ethene gives π-ethene complexes 6-8. In the molecular structure of 7 the C-C vector of the π-ethene ligand is arranged in the equatorial plane of a trigonal bipyramid. Under 1 bar of CO, compound 2 forms a monocarbonyl complex 9, in which an equatorial carbonyl ligand is found in the molecular structure. Iodomethane transforms 2 into pentacoordinate [{2-(diphenylphosphanyl)naphthyl-(C1,P)/iodobis- (trimethylphosphane)cobalt] (10) with retention of the metallacycle. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.