TY - JOUR
T1 - 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)
AU - García-Antón, Jordi
AU - Mathieu, René
AU - Lugan, Noël
AU - Pons Picart, Josefina
AU - Ros, Josep
PY - 2004/5/1
Y1 - 2004/5/1
N2 - The 1,5-bis(3,5-dimethyl-1-pyrazolyl)-3-thiapentane ligand (bdtp) reacts with [Rh(COD)(THF)2][BF4] to give [Rh(COD)(bdtp)][BF4] ([1][BF4]), 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)][BF4] ([2][BF4]) and [Rh(CO)( bdtp -κ3 N, N, S )][BF4] ([3][BF4]). In solution, [2][BF4] exists as a mixture of two isomers, [Rh(CO)2(bdtp -κ2 N, N)]+ ([2a]+) and [Rh(CO)2(bdtp -κ3 N, N, S)]+ ([2b]+; major isomer) rapidly interconverting on the NMR time scale. At room temperature, [2][BF4] easily loses one molecule of carbon monoxide to give [3][BF4]. The latter is prone to react with carbon monoxide to partially regenerate [2][BF4]. 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][BF4] to give the dinuclear complexes [Rh2(bddf)(COD)2] [BF4]2 ([4][BF4]2) and [Rh2(bddo)(COD)2][BF4]2 ([5][BF4]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][BF4]2 results in loss of the COD ligand and carbonylation to give [Rh2(bddf)(CO)4] [BF4]2 ([6][BF4]2). The single-crystal X-ray structures of [3][CF3SO3], [5][BF4]2 and [6][BF4]2 are reported. © 2004 Elsevier B.V. All rights reserved.
AB - The 1,5-bis(3,5-dimethyl-1-pyrazolyl)-3-thiapentane ligand (bdtp) reacts with [Rh(COD)(THF)2][BF4] to give [Rh(COD)(bdtp)][BF4] ([1][BF4]), 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)][BF4] ([2][BF4]) and [Rh(CO)( bdtp -κ3 N, N, S )][BF4] ([3][BF4]). In solution, [2][BF4] exists as a mixture of two isomers, [Rh(CO)2(bdtp -κ2 N, N)]+ ([2a]+) and [Rh(CO)2(bdtp -κ3 N, N, S)]+ ([2b]+; major isomer) rapidly interconverting on the NMR time scale. At room temperature, [2][BF4] easily loses one molecule of carbon monoxide to give [3][BF4]. The latter is prone to react with carbon monoxide to partially regenerate [2][BF4]. 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][BF4] to give the dinuclear complexes [Rh2(bddf)(COD)2] [BF4]2 ([4][BF4]2) and [Rh2(bddo)(COD)2][BF4]2 ([5][BF4]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][BF4]2 results in loss of the COD ligand and carbonylation to give [Rh2(bddf)(CO)4] [BF4]2 ([6][BF4]2). The single-crystal X-ray structures of [3][CF3SO3], [5][BF4]2 and [6][BF4]2 are reported. © 2004 Elsevier B.V. All rights reserved.
KW - Hemilabile ligands
KW - N,S-ligands
KW - Pyrazole
KW - Rhodium(I)
U2 - 10.1016/j.jorganchem.2004.02.014
DO - 10.1016/j.jorganchem.2004.02.014
M3 - Article
VL - 689
SP - 1599
EP - 1608
IS - 9
ER -