| Several carbonyl metal derivatives of Keggin-type polyoxoanions or isopolyoxo-molybdateswere synthesized through the reaction of saturated Keggin-type hetero-polyoxoanionsor isopolyoxomolybdates as the starting resources with carbonyl metal species in the organic or mixed solvent, and characterized by single-crystal X-ray diffraction, spectroscopic, thermal and magnetic properties.(1) Three carbonyl manganese cation salts based on Keggin-type polyoxoanions [Mn(CO)3(CH3CN)3]4SiMo12O40·1.5H2O (1), [Mn(CO)3(CH3CN)3]3HGeMo12O40 (2), [Re(CO)3(CH3CN)3]3PW12O40·CH3CN·1.5H2O (3) were synthesized in mixed solvent, and characterized by single-crystal X-ray diffraction, element analysis, IR, UV spectra. X-ray diffraction show the molecule structure units of the three compounds all consist of [M(CO)3(CH3CN)3]+ (M = Mn or Re) coordination cations and a Keggin-type polyanion.(2) The reaction of (n-Bu4N)4[Mo8O26] and Mn(CO)5Br in the same solvent resulted in two carbonyl manganese derivatives of isopolyoxomolybdates (n-Bu4N)2[{Mn(CO)3 (H2O)}Mo5O16(OCH3)2{Mn(CO)3}] (4) (in N2 atmosphere) and (n-Bu4N)2[Mo6O16 (OCH3)2{HOCH2C(CH2O)3}2{Mn(CO)3}2] (5) (in the existence of C(CH2OH)4), which were characterized by single-crystal X-ray diffraction, IR and UV spectra. The former contains a monovacant Lindqvist-type [Mo5O16(OCH3)2]4- anion, supported two carbonyl manganese groups through oxygen atoms. The latter can be viewed as being made of two crystallographically independent [Mo3O8(OCH3){HOCH2C(OCH2)3} {MnCO)3}]- units connected through two near-linear Mn-O-Mn bridges.(3) The compound [DMAH]4{[Mn(DMF)4]2[Mn4(DMF)2(α-B-HPW9O34)2]} (6) was solvothermally synthesized and characterized by single-crystal X-ray diffraction, IR and UV spectra.
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