Syntheses of cationic tri- and di-carbonyl complexes of manganese(I) with diphosphines from the appropriate neutral bromocarbonyls
Syntheses of cationic tri- and di-carbonyl complexes of manganese(I) with diphosphines from the appropriate neutral bromocarbonyls
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由适当的中性溴羰基合成锰(I)与二膦的阳离子三羰基和二羰基络合物
DOI：
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发表时间：
1981
期刊：
影响因子：
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通讯作者：
V. Riera
中科院分区：
文献类型：
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作者：
F. Bombin;G. A. Carriedo;J. Miguel;V. Riera
配合物fac-[MnBr(CO)3(L - L)][L - L = Ph2P(CH2)nPPh2, n= 1 （dppm）或2(dppe)]与磷给体L反应得到顺式，顺式-[MnBr(CO)2(L - L)L]配合物。这些中性二羰基被NO2或[NO][PF6]氧化为不稳定的阳离子物种trans-[MnBr(CO)2(L - L)L]+，可分离为六氟磷酸盐，经肼还原后生成中性的trans-[MnBr(CO)2(L - L)L]。用TI[PF6]取代顺式、顺式或反式[MnBr(CO)2(L - L)L]中的溴配体，在另一配体L ‘ （N或P供体）存在的情况下，分别形成顺式、顺式或反式[Mn(CO)2(L - L)LL ’][PF6]，或者如果L ' = CO，则形成mer-[Mn(CO)3(L - L)L][PF6]。然而，使用Ag[CIO4]作为卤素萃取剂，无论使用中性溴羰基异构体，都可以得到顺式、顺式阳离子二羰基（或mer三羰基）的高氯酸盐。
Reaction of the complexes fac-[MnBr(CO)3(L–L)][L–L = Ph2P(CH2)nPPh2, n= 1 (dppm) or 2 (dppe)] with phosphorus-donor ligands, L, leads to the complexes cis,cis-[MnBr(CO)2(L–L)L]. These neutral dicarbonyls are oxidized by NO2 or [NO][PF6] to the unstable cationic species trans-[MnBr(CO)2(L–L)L]+ which may be isolated as hexafluorophosphate salts and which lead to the neutral trans-[MnBr(CO)2(L–L)L] when reduced by hydrazine. Replacement of the bromo-ligand in either cis,cis- or trans-[MnBr(CO)2(L–L)L], using TI[PF6] in the presence of another ligand L′(N or P donor), results in the formation of cis,cis- or trans-[Mn(CO)2(L–L)LL′][PF6] respectively, or of mer-[Mn(CO)3(L–L)L][PF6] if L′= CO. However, using Ag[CIO4] as the halogen abstracter, the perchlorate salts of the cis,cis-cationic dicarbonyls (or the mer tricarbonyls) are obtained regardless of the neutral bromocarbonyl isomer used.