Bimetallic systems. Part 17. Synthesis of Group 6 metal(0)–copper(I)–silver(I), or –gold(I) complexes with two Ph2PCH2PPh2(dppm) bridging ligands: crystal structure of [(OC)2W(µ-CO)(µ-dppm)2(µ-Cl)Cu]·CH2Cl2
Bimetallic systems. Part 17. Synthesis of Group 6 metal(0)–copper(I)–silver(I), or –gold(I) complexes with two Ph2PCH2PPh2(dppm) bridging ligands: crystal structure of [(OC)2W(µ-CO)(µ-dppm)2(µ-Cl)Cu]·CH2Cl2
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双金属系统。第 17 部分。具有两个 Ph2PCH2PPh2(dppm) 桥连配体的第 6 族金属(0)–铜(I)–银(I)或–金(I)配合物的合成：[(OC)2W( 的晶体结构) µ-CO)(µ-dppm)2(µ-Cl)Cu]CH2Cl2
DOI：
10.1039/dt9870000769
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发表时间：
1987
期刊：
影响因子：
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通讯作者：
M. Thornton
中科院分区：
文献类型：
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作者：
A. Blagg;B. Shaw;M. Thornton
用CuI、AgI或AuI化合物处理fac-或mer-[M（CO）3（dppm-PP′）（dppm-P）]（M = Cr、Mo或W; dppm = Ph 2 PCH 2 PPh 2）有时会引起开环，得到杂环化合物，但在其他情况下，会发生快速的氧化还原反应或更复杂的过程。用CuX（X = Cl或I）处理mer-[M（CO）3（dppm-PP′）（dppm-P）]（M = Cr、Mo或W）得到中等产率的[（OC）2 M（μ-CO）（μ-dppm）2（μ-X）Cu]，而用CuX处理fac-[M（CO）3（dppm-PP′）（dppm-P）]（M = Mo或W）只得到CuI-dppm物质。fac-或mer-[M（CO）_3（dppm-PP′）（dppm-P）]被AgNO_3氧化，但通常与[Ag_4Cl_4（PPh_3）_4]反应，得到一个dppm桥连的M-Ag配合物。[Mo（CO）_3（dppm-PP′）（dppm-P）]与[Ag_4Cl_4（PPh_3）_4]反应生成不稳定的配合物[（OC）_3Mo（μ-dppm）_2AgCl]，~（31）P-{1H} n.m.r.其光谱随温度而变化。用[Ag（PPh 3）（CN）]处理fac-or mer-[M（CO）3（dppm-PP′）（dppm-P）]得到稳定的杂原子[（OC）3 M（µ-dppm）2Ag（CN）]型配合物（M = Cr，Mo，or W）。mer-[M（CO）3（dppm-PP′）（dppm-P）]（M = Mo或W）与[Au（PPh 3）Cl]反应生成[（OC）3 M（μ-dppm）2AuCl]，而fac-[M（CO）3（dppm-PP′）（dppm-P）]与[Au（PPh 3）Cl]反应生成一种复杂的混合物。测定了[（OC）2 W（μ-CO）（μ-dppm）2（μ-Cl）Cu]·CH 2Cl 2的单斜晶系晶体结构，空间群为P21/c，a= 1076.0（2），B= 2513.2（4），c= 2067.5（3）pm，β= 112.62（1）°，Z= 4，最终R因子为0.0359，共观察到6138个反射峰.结构表明两个金属中心[W-Cu 275.9（4）pm]几乎对称地由氯[W-Cl 259.2（5），Cu-Cl 255.3（5）pm]桥接，并由CO半桥接。
Treatment of fac- or mer-[M (CO)3(dppm-PP′)(dppm-P)](M = Cr, Mo, or W; dppm = Ph2PCH2PPh2) with CuI, AgI, or AuI compounds sometimes induced ring-opening to give heterobimetallic complexes, but in other cases rapid redox reactions, or more complicated processes, occurred. Treatment of mer-[M(CO)3(dppm-PP′)(dppm-P)](M = Cr, Mo, or W) with CuX (X = Cl or I) gave [(OC)2M (µ-CO)(µ–dppm)2(µ-X)Cu] in moderate yields, whereas treatment of fac-[M(CO)3(dppm-PP′)(dppm-P)](M = Mo or W) with CuX gave only CuI-dppm species. fac- or mer-[M(CO)3(dppm-PP′)(dppm-P)] were oxidised by AgNO3, but in general reacted with [Ag4Cl4(PPh3)4] to give M–Ag complexes with one bridging dppm. However, treatment of mer-[Mo(CO)3(dppm-PP′)(dppm-P)] with [Ag4Cl4(PPh3)4] gave an unstable complex [(OC)3Mo(µ-dppm)2 AgCl], the 31P-{1H} n.m.r. spectra of which varied with temperature. Treatment of fac-or mer-[M(CO)3(dppm-PP′)(dppm-P)] with [Ag(PPh3)(CN)] gave stable, heterobimetallic, complexes of the type [(OC)3M(µ-dppm)2Ag(CN)](M = Cr, Mo, or W). Reaction between mer-[M(CO)3(dppm-PP′)(dppm-P)](M = Mo or W) and [Au(PPh3)Cl] gave [(OC)3M (µ-dppm)2AuCl], whereas a complex mixture of unidentified products was formed on treating fac-[M(CO)3(dppm-PP′)(dppm-P)] with [Au(PPh3)Cl]. The molecular structure of [(OC)2W(µ-CO)(µ-dppm)2(µ-Cl)Cu]·CH2Cl2 was determined from a monoclinic crystal of space group P21/c, with a= 1 076.0(2), b= 2 513.2(4), c= 2 067.5(3) pm, β= 112.62(1)°, and Z= 4; final R factor 0.0359 for 6 138 observed reflections. The structure shows that the two metal centres [W–Cu 275.9(4) pm] are almost symmetrically bridged by chlorine [W–Cl 259.2(5), Cu–Cl 255.3(5) pm] and semibridged by CO.