Core Conversion Reactions of the Cubane-Type Metal-Sulfido Clusters: Shape Shift, Contraction, and Expansion of the MM'Re Cubanes (M = Ir, Rh, Ru; M' = Pt, Pd)
Core Conversion Reactions of the Cubane-Type Metal-Sulfido Clusters: Shape Shift, Contraction, and Expansion of the MM'Re Cubanes (M = Ir, Rh, Ru; M' = Pt, Pd)
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古巴烷型金属硫簇团簇的核心转化反应：MMRe 古巴烷的形状变化、收缩和膨胀（M = Ir、Rh、Ru；M = Pt、Pd）
DOI：
10.1021/ic100339f
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发表时间：
2010
影响因子：
4.6
通讯作者：
Yasushi Mizobe
中科院分区：
文献类型：
--
作者：
Rie Shibata;Hidetake Seino;Shunpei Fujii;Yasushi Mizobe
Treatment of incomplete cubane-type clusters [(Cp*M){Re(L)}2(μ3-S)(μ2-S)3] (M = Ir (1a), Rh (1b); Cp* = η5-C5Me5; L = S2C2(SiMe3)2) and [{(Pmb)Ru}{Re(L)}2(μ3-S)(μ2-S)3] (Pmb = η6-C6Me5H) with 1 equiv of [Pt(PPh3)3] gave tetranuclear tetra(sulfido) clusters having raft-type cores, [(Cp*M){Pt(PPh3)2}{Re(L)}2(μ3-S)4] (M = Ir (3a), Rh) and [{(Pmb)Ru}{Pt(PPh3)2}{Re(L)}2(μ3-S)4], which presents a sharp contrast to the reactions with [Pd(PPh3)4] reported previously, affording the cubane-type clusters [(Cp*M){Pd(PPh3)}{Re(L)}2(μ3-S)4] (M = Ir (2a), Rh) and [{(Pmb)Ru}{Pd(PPh3)}{Re(L)}2(μ3-S)4]. The reactions of2awith diphosphinesP2resulted in the conversion of its cubane-type core into the analogous raft-type frameworks, forming [(Cp*Ir){Pd(P2)}{Re(L)}2(μ3-S)4] (P2=cis-Ph2PCHCHPPh2(6), Ph2PCH2CH2PPh2, Ph2PCH2CH2CH2PPh2). On the other hand, when2was allowed to react with Ph2PCH2PPh2(dppm) asP2, the trinuclear tri(sulfido) cluster [(Cp*Ir){Re(L)}2(μ3-S)2(μ2-S)(μ2-dppm)] (9a) was obtained. Alternatively, this cluster9aand its Rh analogue9bwere derived from the incomplete cubane-type clusters1aand1bby treatment with dppm. It has also been found that further treatment of the cubane-type cluster2awith excess [Pd(PPh3)4] affords the heptanuclear tetra(sulfido) cluster [(Cp*Ir){Pd(PPh3)}4Re2(μ3-L)2(μ3-S)4] (10). The detailed structures have been determined by the X-ray analyses for3a,6,9a, and10.
Treatment of incomplete cubane-type clusters [(Cp*M){Re(L)}2(μ3-S)(μ2-S)3] (M = Ir (1a), Rh (1b); Cp* = η5-C5Me5; L = S2C2(SiMe3)2) and [{(Pmb)Ru}{Re(L)}2(μ3-S)(μ2-S)3] (Pmb = η6-C6Me5H) with 1 equiv of [Pt(PPh3)3] gave tetranuclear tetra(sulfido) clusters having raft-type cores, [(Cp*M){Pt(PPh3)2}{Re(L)}2(μ3-S)4] (M = Ir (3a), Rh) and [{(Pmb)Ru}{Pt(PPh3)2}{Re(L)}2(μ3-S)4], which presents a sharp contrast to the reactions with [Pd(PPh3)4] reported previously, affording the cubane-type clusters [(Cp*M){Pd(PPh3)}{Re(L)}2(μ3-S)4] (M = Ir (2a), Rh) and [{(Pmb)Ru}{Pd(PPh3)}{Re(L)}2(μ3-S)4]. The reactions of2awith diphosphinesP2resulted in the conversion of its cubane-type core into the analogous raft-type frameworks, forming [(Cp*Ir){Pd(P2)}{Re(L)}2(μ3-S)4] (P2=cis-Ph2PCHCHPPh2(6), Ph2PCH2CH2PPh2, Ph2PCH2CH2CH2PPh2). On the other hand, when2was allowed to react with Ph2PCH2PPh2(dppm) asP2, the trinuclear tri(sulfido) cluster [(Cp*Ir){Re(L)}2(μ3-S)2(μ2-S)(μ2-dppm)] (9a) was obtained. Alternatively, this cluster9aand its Rh analogue9bwere derived from the incomplete cubane-type clusters1aand1bby treatment with dppm. It has also been found that further treatment of the cubane-type cluster2awith excess [Pd(PPh3)4] affords the heptanuclear tetra(sulfido) cluster [(Cp*Ir){Pd(PPh3)}4Re2(μ3-L)2(μ3-S)4] (10). The detailed structures have been determined by the X-ray analyses for3a,6,9a, and10.