Reaction of the Mo3S4 Cluster with Dimethylacetylenedicarboxylate: An ESR-Active Cluster and an Organometallic Cluster Formed by 
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- 作者：Yasuhiro Ide ; Takashi Shibahara
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：January 22, 2007
- 年：2007
- 卷：46
- 期：2
- 页码：357 - 359
- 全文大小：112K
- 年卷期：v.46,no.2(January 22, 2007)
- ISSN：1520-510X
文摘
A seven-electron cluster [Mo3(
3-S){3-SC(CO2CH3)=C(CO2CH3)S}{-SC(CO2CH3)=CH(CO2CH3)}(dtp)3(-OAc)] [2, S2P(OC2H5)2-; dtp = diethyldithiophosphate] and an organometallic cluster[Mo3(3-S){3-SC(CO2CH3)=C(CO2CH3)S}{-SC(CO2CH3)CH(OCH3)(CO2)}(dtp)2(CH3OH)(-OAc)](Mo-C) (3) were obtained byreaction in methanol of the sulfur-bridged trinuclear complex [Mo3(3-S)(-S)3(dtp)3(CH3CN)(-OAc)] (1) with dimethylacetylenedicarboxylate (DMAD). The X-ray structures of 2 and 3 revealed theadduct formation of two DMAD molecules to the respective Mo3S4cores. 2 is paramagnetic and obeys the Curie-Weiss law: theeff value at 300 K is 1.90 B. The electron spin resonance signalwas observed at 173 K. The density functional theory calculationof 2 demonstrated that the main components of the singly occupiedmolecular orbitals of 
and 
spins are Mo d electrons and themain components of lowest unoccupied molecular orbitals are ofMo and the olefin moiety with one C-S bond. A one-electronreversible oxidation process of 2 was observed at E1/2 = -0.11 Vvs Fc/Fc+. The electronic spectrum of 2 has a peak at 468 nm (
= 2170 M-1 cm-1) and shoulders at 640 (918) and 797 (605)nm, and 3 has shoulders at 441 (1740) and 578 (625) nm and adistinct peak at 840 (467) nm. An intermediate [Mo3(3-S){3-SC(CO2CH3)=C(CO2CH3)S}{-SC(CO2CH3)=CH(CO2CH3)}(dtp)3(-OAc)]+ (4) is tentatively suggested: a one-electron reductionof 4 gives 2, and a nucleophilic conjugate addition of CH3O- tothe ,-unsaturated carbonyl group of 4 gives 3.
3-S){3-SC(CO2CH3)=C(CO2CH3)S}{-SC(CO2CH3)=CH(CO2CH3)}(dtp)3(-OAc)] [2, S2P(OC2H5)2-; dtp = diethyldithiophosphate] and an organometallic cluster[Mo3(3-S){3-SC(CO2CH3)=C(CO2CH3)S}{-SC(CO2CH3)CH(OCH3)(CO2)}(dtp)2(CH3OH)(-OAc)](Mo-C) (3) were obtained byreaction in methanol of the sulfur-bridged trinuclear complex [Mo3(3-S)(-S)3(dtp)3(CH3CN)(-OAc)] (1) with dimethylacetylenedicarboxylate (DMAD). The X-ray structures of 2 and 3 revealed theadduct formation of two DMAD molecules to the respective Mo3S4cores. 2 is paramagnetic and obeys the Curie-Weiss law: theeff value at 300 K is 1.90 B. The electron spin resonance signalwas observed at 173 K. The density functional theory calculationof 2 demonstrated that the main components of the singly occupiedmolecular orbitals of and spins are Mo d electrons and themain components of lowest unoccupied molecular orbitals are ofMo and the olefin moiety with one C-S bond. A one-electronreversible oxidation process of 2 was observed at E1/2 = -0.11 Vvs Fc/Fc+. The electronic spectrum of 2 has a peak at 468 nm (= 2170 M-1 cm-1) and shoulders at 640 (918) and 797 (605)nm, and 3 has shoulders at 441 (1740) and 578 (625) nm and adistinct peak at 840 (467) nm. An intermediate [Mo3(3-S){3-SC(CO2CH3)=C(CO2CH3)S}{-SC(CO2CH3)=CH(CO2CH3)}(dtp)3(-OAc)]+ (4) is tentatively suggested: a one-electron reductionof 4 gives 2, and a nucleophilic conjugate addition of CH3O- tothe ,-unsaturated carbonyl group of 4 gives 3.