TY - JOUR
T1 - Diruthenium half-sandwich complexes containing one μ-E2 (E = S, Se) unit and two chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligands
T2 - Reactivity studies with methyl acetylene carboxylates
AU - Wu, De Hong
AU - Xu, Bao Hua
AU - Li, Yi Zhi
AU - Yan, Hong
PY - 2007/12/3
Y1 - 2007/12/3
N2 - [(p-Cymene)RuCl2]2 reacts with Li2[S 2C2(B10H10)] in the presence of excess chalcogen elements to generate dinuclear complexes (p-cymene)Ru(μ- E2)Ru(S2C2B10H10) 2, 1S (E = S) and 1Se (E = Se), in which one E-E bridge between the two ruthenium atoms and two chelating 1,2-dicarba-closo-dodecaborane-1,2- dithiolate ligands are present. In 1S and 1Se, one ruthenium atom is surrounded by six chalcogen atoms in a geometry of distorted octahedron and electron-deficient (16e). Treatment of 1S and 1Se with methyl acetylene carboxylates affords addition complexes, (p-cymene)Ru(μ-E2)Ru- (S2C2B10H10)2(R 1C=CR2) (R1 = H (CO2Me), R 2 = CO2Me (H), 2S, 2Se (3S, 3Se); R1 = R 2 = CO2Me, 4S, 4Se). The terminal alkyne leads to two geometrical isomers that interconvert upon heating. Alkyne addition occurs at sulfur atoms of two different dithiolate ligands that leads to a change of 16e Ru(IV) in 1S and 1Se to 18e Ru(II) in 2S-4S and 2Se-4Se, respectively. The complexes were characterized by IR, MS, NMR spectroscopy, and microanalysis. X-ray structural analyses were performed on 1S-4S and 2Se-4Se.
AB - [(p-Cymene)RuCl2]2 reacts with Li2[S 2C2(B10H10)] in the presence of excess chalcogen elements to generate dinuclear complexes (p-cymene)Ru(μ- E2)Ru(S2C2B10H10) 2, 1S (E = S) and 1Se (E = Se), in which one E-E bridge between the two ruthenium atoms and two chelating 1,2-dicarba-closo-dodecaborane-1,2- dithiolate ligands are present. In 1S and 1Se, one ruthenium atom is surrounded by six chalcogen atoms in a geometry of distorted octahedron and electron-deficient (16e). Treatment of 1S and 1Se with methyl acetylene carboxylates affords addition complexes, (p-cymene)Ru(μ-E2)Ru- (S2C2B10H10)2(R 1C=CR2) (R1 = H (CO2Me), R 2 = CO2Me (H), 2S, 2Se (3S, 3Se); R1 = R 2 = CO2Me, 4S, 4Se). The terminal alkyne leads to two geometrical isomers that interconvert upon heating. Alkyne addition occurs at sulfur atoms of two different dithiolate ligands that leads to a change of 16e Ru(IV) in 1S and 1Se to 18e Ru(II) in 2S-4S and 2Se-4Se, respectively. The complexes were characterized by IR, MS, NMR spectroscopy, and microanalysis. X-ray structural analyses were performed on 1S-4S and 2Se-4Se.
UR - http://www.scopus.com/inward/record.url?scp=37249048882&partnerID=8YFLogxK
U2 - 10.1021/om7008556
DO - 10.1021/om7008556
M3 - Article
AN - SCOPUS:37249048882
SN - 0276-7333
VL - 26
SP - 6300
EP - 6306
JO - Organometallics
JF - Organometallics
IS - 25
ER -