TY - JOUR
T1 - Synthetic and X-ray structural and reactivity studies of Cp*Ru IV complexes containing bidentate dithiocarbonate, xanthate, carbonate, and phosphinate ligands (Cp* = η5-C 5Me5)
AU - Tay, Elaine Phuay Leng
AU - Seah, Ling Kuan
AU - Weng, Kee Leong
AU - Lai, Yoong Goh
PY - 2007/2/19
Y1 - 2007/2/19
N2 - The reaction of [Cp*RuCl2]2 (1; Cp* = η5-C5Me5) with tetraalkyldithiuram disulfides (R2NC(S)SS(S)CNR2, R = Me, Et), isopropylxanthic disulfide ([iPrOC(S)S]2), and bis(thiophosphoryl) disulfide ([(iPrO)2P(S)S]2) led to the isolation of dark-red crystalline solids of Cp*Ru IVCl2(η2-dithiolate) complexes [dithiolate = S2CNR2, DTCR (2a, R = Me; 2b, R = Et), S 2COiPr (3), and S2P(iPrO) 2 (4)]. Dichlorido substitution in 2 and 3 with DTCEt and S2COiPr anions yielded RuIV derivatives containing bis(DTC) and mixed DTC-dithiocarbonate ligands. These are the first organoruthenium complexes of such ligands. The reaction of monophosphines with 2a resulted in monochlorido substitution, whereas the analogous reaction with 3 resulted in displacement of both chlorido ligands and reduction of the metal center to RuII. Reduction at Ru was also observed in the reaction of 2a with [CpCr(CO)3]2. Of these complexes, only 2 and 3 are air-stable in the solid state for an extended period. All of the complexes have been spectrally characterized, and selected compounds are also crystallographically characterized.
AB - The reaction of [Cp*RuCl2]2 (1; Cp* = η5-C5Me5) with tetraalkyldithiuram disulfides (R2NC(S)SS(S)CNR2, R = Me, Et), isopropylxanthic disulfide ([iPrOC(S)S]2), and bis(thiophosphoryl) disulfide ([(iPrO)2P(S)S]2) led to the isolation of dark-red crystalline solids of Cp*Ru IVCl2(η2-dithiolate) complexes [dithiolate = S2CNR2, DTCR (2a, R = Me; 2b, R = Et), S 2COiPr (3), and S2P(iPrO) 2 (4)]. Dichlorido substitution in 2 and 3 with DTCEt and S2COiPr anions yielded RuIV derivatives containing bis(DTC) and mixed DTC-dithiocarbonate ligands. These are the first organoruthenium complexes of such ligands. The reaction of monophosphines with 2a resulted in monochlorido substitution, whereas the analogous reaction with 3 resulted in displacement of both chlorido ligands and reduction of the metal center to RuII. Reduction at Ru was also observed in the reaction of 2a with [CpCr(CO)3]2. Of these complexes, only 2 and 3 are air-stable in the solid state for an extended period. All of the complexes have been spectrally characterized, and selected compounds are also crystallographically characterized.
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U2 - 10.1021/ic061781t
DO - 10.1021/ic061781t
M3 - Article
AN - SCOPUS:33847710336
SN - 0020-1669
VL - 46
SP - 1440
EP - 1450
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 4
ER -