‘One-pot’ synthesis of two molybdenum/ tungsten (VI)–copper(I) mixed metal clusters under catalysis of 1,10-phenathroline

Publication year: 2011
Source: Inorganic Chemistry Communications, In Press, Accepted Manuscript, Available online 13 June 2011

Qiong-Hua, Jin , Ye-Lan, Xiao , Ke-Yi, Hu , Zhong-Feng, Li , Rong, Wang , …

Under the catalysis of 1,10-phenathroline (phen), (NH4)2M’S4 (M’=Mo,W) reacts with CuSCN and dppm in mixed solvent MeCN/DMF (1:1) to yield two saddle–shaped clusters [WS4Cu4(SCN)2 (dppm)3 ]·3DMF·2CH3CN (1) and [MoS4Cu4(SCN)2 (dppm)3]·4DMF (2) (dppm=bis (diphenylphosphino) methane). Compounds 1–2 were characterized by elemental analysis, IR, UV-Vis, 1H NMR, 31P NMR, and single-crystal X-ray diffraction. Each [M’S4]2- (M’=Mo, W) anion coordinates to four Cu atoms through four bridging S atoms, and all S atoms are coordinated with two Cu atoms. In each cluster the four Cu atoms are almost in one plane, and the M’ atom is above the plane. Cluster 1 was characterized…

Under the catalysis of 1,10-phenathroline, (NH4)2M’S4 (M’=Mo,W) reacts with CuSCN and dppm in MeCN/DMF (1:1) mixed solvent to yield two saddle–shaped clusters [WS4Cu4(SCN)2 (dppm)3 ]·3DMF·2CH3CN (1) and [MoS4Cu4(SCN)2 (dppm)3]·4DMF (2) (dppm=bis (diphenylphosphino) methane). Compounds 1–2 were characterized by IR, UV-Vis, 1H NMR, 31P NMR, and single-crystal X-ray diffraction. Highlights: ► Under the catalysis of 1,10-phenathroline (phen), two saddle–shaped clusters [WS4Cu4(SCN)2 (dppm)3 ]·3DMF·2CH3CN (1) and [MoS4Cu4(SCN)2 (dppm)3]·4DMF (2) (dppm=bis (diphenylphosphino) methane) were synthesized and characterized by IR, UV-Vis, 1H NMR, 31P NMR, and single-crystal X-ray diffraction. ► The synthesis method using phen as the catalysis was confirmed to be an effective strategy of synthesizing new mixed metal clusters. ► The possible catalysis mechanism of phenathroline is discussed. ► From the structures of 1–4, we can see that the skeletons of Mo/W-Cu/Ag clusters are affected not only by the coordinated anions but also by the coordination number of metal atom. Compared with Mo/W-Ag clusters, Mo/W-Cu clusters of novel skeletons are more difficult to be obtained since Cu atom has fewer coordination modes.
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