Synthesis of the 13-vertex rhodacarborane anion [4-(1,2:5,6-η-cod )-closo -4,1,6-RhC2B10H12]- and its reactions with electrophiles
Synthesis of the 13-vertex rhodacarborane anion [4-(1,2:5,6-η-cod )-closo -4,1,6-RhC2B10H12]- and its reactions with electrophiles
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13-顶点罗达碳硼烷阴离子[4-(1,2:5,6-η-cod)-closo-4,1,6-RhC2B10H12]-的合成及其与亲电子试剂的反应
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发表时间：
2005
期刊：
影响因子：
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通讯作者：
F. Stone
中科院分区：
文献类型：
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作者：
B. Hodson;T. McGrath;F. Stone
在THF （THF =四氢呋喃）中，萘钠还原clo_2 -1,2- c_2 - b_1 - h_2，然后加入[Rh 2 (μ-Cl) 2 (cod) 2] （cod = 1,2:5,6-η-环己二烯）和[N(PPh3) 2]Cl，得到单阴离子13顶点的红碳硼烷[N(PPh3) 2][4-(cod)- clo_2 -4,1,6- rhc 2 b_1 - h_2](2)。治疗化合物2的来源阳离子{铜(PPh 3)} + {Rh (PPh 3) 2} + {Rh (cod)} +和{RuCl (PPh 3) 2} +产量,分别中性双金属物种[4 - (cod) 3、4、7 -{铜(PPh 3)} 3, 7 - 2 -close-4 (mh), 1, 6-RhC 2 B 1 0 H 1 0], [4 - (cod) 3、8 - {Rh (PPh 3) 2} 3、8 -(μ- H) 2 -closo4, 1, 6-RhC 2 B 1 0 H 1 0], [4 - (cod) 3、8 - {Rh (cod)} 3、8 -(μ- H) 2-closo-4, 1, 6-RhC 2 B 1 0 H 1 0),和[4 - (cod) 3、7、8 - {RuCl (PPh 3) 2} 3、7、8 -(μ- H) 3-closo-4, 1, 6-RhC 2 B 1 0 H 9],其中只有铜衍生物有金属-金属键。此外，2与cf3so3h的反应导致环二烯配体质子化，同时铑中心氧化，生成表面上有16个电子的Rh I I I I化合物[4-(1-3-η 3- c - 8h13)-closo-4,1,6- rhc2b10h12]，该化合物被C-H…相互作用。或者，在THF存在的情况下，用氢化试剂处理2会导致笼形BH顶点的取代，形成两性离子络合物[4-(cod)-7-{O(CH 2) 4}- close -4,1,6- rhc 2 b1 0 H 11]。
Reduction of closo-1,2-C 2 B 1 0 H 1 2 , with sodium naphthalide in THF (THF = tetrahydrofuran), followed by addition of [Rh 2 (μ-Cl) 2 (cod) 2 ] (cod = 1,2:5,6-η-cyclooctadiene) and [N(PPh 3 ) 2 ]Cl, affords the monoanionic 13-vertex rhodacarborane [N(PPh3) 2 ][4-(cod)-closo-4,1,6-RhC 2 B 1 0 H 1 2 ] (2). Treatment of compound 2 with sources of the cations {Cu(PPh 3 )} + , {Rh(PPh 3 ) 2 } + , {Rh(cod)} + , and {RuCl(PPh 3 ) 2 } + yields, respectively, the neutral bimetallic species [4-(cod)-3,4,7-{Cu(PPh 3 )}-3,7-(m-H) 2 -close-4,1,6-RhC 2 B 1 0 H 1 0 ], [4-(cod)-3,8-{Rh(PPh 3 ) 2 }-3,8-(μ-H) 2 -closo4,1,6-RhC 2 B 1 0 H 1 0 ], [4-(cod)-3,8-{Rh(cod)}-3,8-(μ-H)2-closo-4,1,6-RhC 2 B 1 0 H 1 0 ], and [4-(cod)-3,7,8-{RuCl(PPh 3 ) 2 }-3,7,8-(μ-H)3-closo-4,1,6-RhC 2 B 1 0 H 9 ], of which only the copper derivative has a metal-metal bond. In addition, the reaction of 2 with CF 3 SO 3 H results in protonation of the cyclooctadiene ligand with concomitant oxidation of the rhodium center, yielding the ostensibly 16-electron Rh I I I compound [4-(1-3-η 3 -C 8 H 1 3 )-closo-4,1,6-RhC 2 B 1 0 H 1 2 ], which is stabilized by a C-H...Rh agostic interaction. Alternatively, treatment of 2 with hydride-ing reagents in the presence of THF results in substitution at a cage BH vertex, forming the zwitterionic complex [4-(cod)-7-{O(CH 2 ) 4 }-closo-4,1,6-RhC 2 B 1 0 H 1 1 ].