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• W2076592008 abstract "The 1,5-bis(3,5-dimethyl-1-pyrazolyl)-3-thiapentane ligand ( bdtp ) reacts with [Rh(COD)(THF) 2 ][BF 4 ] to give [Rh(COD)( bdtp )][BF 4 ] ([ 1 ][BF 4 ]), which is fluxional in solution on the NMR time scale. Its further treatment with carbon monoxide leads to a displacement of the 1,5-cyclooctadiene ligand, generating a mixture of two complexes, namely, [Rh(CO) 2 ( bdtp )][BF 4 ] ([ 2 ][BF 4 ]) and [Rh(CO)( bdtp -κ 3 N , N , S )][BF 4 ] ([ 3 ][BF 4 ]). In solution, [ 2 ][BF 4 ] exists as a mixture of two isomers, [Rh(CO) 2 ( bdtp -κ 2 N , N )] + ([ 2a ] + ) and [Rh(CO) 2 ( bdtp -κ 3 N , N , S )] + ([ 2b ] + ; major isomer) rapidly interconverting on the NMR time scale. At room temperature, [ 2 ][BF 4 ] easily loses one molecule of carbon monoxide to give [ 3 ][BF 4 ]. The latter is prone to react with carbon monoxide to partially regenerate [ 2 ][BF 4 ]. The ligands 1,2-bis[3-(3,5-dimethyl-1-pyrazolyl)-2-thiapropyl]benzene ( bddf ) and 1,8-bis(3,5-dimethyl-1-pyrazolyl)-3,6-dithiaoctane ( bddo ) are seen to react with two equivalents of [Rh(COD)(THF) 2 ][BF 4 ] to give the dinuclear complexes [Rh 2 ( bddf )(COD) 2 ][BF 4 ] 2 ([ 4 ][BF 4 ] 2 ) and [Rh 2 ( bddo )(COD) 2 ][BF 4 ] 2 ([ 5 ][BF 4 ] 2 ), respectively. In such complexes, the ligand acts as a double pincer holding two rhodium atoms through a chelation involving S and N donor atoms. Bubbling carbon monoxide into a solution of [ 4 ][BF 4 ] 2 results in loss of the COD ligand and carbonylation to give [Rh 2 ( bddf )(CO) 4 ][BF 4 ] 2 ([ 6 ][BF 4 ] 2 ). The single-crystal X-ray structures of [ 3 ][CF 3 SO 3 ], [ 5 ][BF 4 ] 2 and [ 6 ][BF 4 ] 2 are reported." @default.
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• W2076592008 date "2004-05-01" @default.
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• W2076592008 title "Coordination properties of N2S (1,5-bis(3,5-dimethyl-1-pyrazolyl)-3-thiapentane) or N2S2 (1,8-bis(3,5-dimethyl-1-pyrazolyl)-3,6-dithiaoctane or 1,2-bis[3-(3,5-dimethyl-1-pyrazolyl)-2-thiapropyl]benzene) donor ligands toward Rh(I)" @default.
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• W2076592008 doi "https://doi.org/10.1016/j.jorganchem.2004.02.014" @default.
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