Merging Organometallic Chemistry with Polyoxometalate Chemistry

• Published in: Chemistry : a European journal Vol. 6; no. 7; pp. 1184 - 1192
• Main Authors: Gouzerh, Pierre, Villanneau, Richard, Delmont, Renaud, Proust, Anna
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 03.04.2000; WILEY‐VCH Verlag
• Subjects: manganese; molybdenum; organometallic oxides; polyoxometalates; rhenium
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/(SICI)1521-3765(20000403)6:7<1184::AID-CHEM1184>3.0.CO;2-B

A series of polyoxomolybdate‐incorporated organometallic complexes has been obtained by reaction of [MBr(CO)5] or solvated {M(CO)3}+ ions (M=Mn or Br) with (nBu4N)2[Mo2O7] in methanol, sometimes in the presence of triols of the type RC(CH2OH)3 (R=Me or CH2OH). Their molecular structures are related to those of previously described polyoxoalkoxomolybdates through the formal replacement of fac‐{MoO2(OR)}+ units by topologically equivalent fac‐{M(CO)3}+ units. Representative pairs of structurally related clusters include [Mo2O6(OMe)4{Re(CO)3}2]2− and [Mo4O10(OMe)6]2−, [Mo2O4{MeC(CH2O)3}2{Mn(CO)3}]− and [Mo3O6(OMe){MeC(CH2O)3}2]−, [Mo2O4{HOCH2C(CH2O)3}2{Mn(CO)3}2] and [Mo4O8(OEt)2{MeC(CH2O)3}2], [Mo6O16(OMe)2{MeC(CH2O)3}2{Mn(CO)3}2]2− and [Mo8O20(OMe)4{MeC(CH2O)3}2]2−. Although the frameworks of the majority of derivatives are based on tetranuclear units which display the common rhomb‐like structure, the alternative cubane‐type arrangement is observed in [Mo2O5(OMe)5{M(CO)3}2]−.