Zusammenfassung
The molecular structure Of [CP*2Mo2P2S3] (1; CP* =eta(5)-C5Me5) has been reinvestigated. In DFT studies a series of various positional isomers A-E have been calculated for the model complex [(C5H5)(2)Mo2P2S3]. The energetically favored isomer [CP*Mo-2(2)(mu,eta(2:2)-PS)(2)(mu-S)] (1B) reacts with W(CO)(5)THF to give [CP*2Mo2P2S3 center dot W(CO)(5)](2). X-ray diffraction analysis of 2 confirms ...
Zusammenfassung
The molecular structure Of [CP*2Mo2P2S3] (1; CP* =eta(5)-C5Me5) has been reinvestigated. In DFT studies a series of various positional isomers A-E have been calculated for the model complex [(C5H5)(2)Mo2P2S3]. The energetically favored isomer [CP*Mo-2(2)(mu,eta(2:2)-PS)(2)(mu-S)] (1B) reacts with W(CO)(5)THF to give [CP*2Mo2P2S3 center dot W(CO)(5)](2). X-ray diffraction analysis of 2 confirms the presence Of two eta(2:2)-PS dumbbells and one singly bridging sulfur ligand, the W(CO)(5) fragment being coordinated at one of the P atoms. Arrangement B is also found in the structure of the diadduct [CP degrees 2Mo2P2S3-{W(CO)(5)}(2)] (3; Cp degrees = t-BUMe2C5H2), which is more stable than its Cp* analogue. P-31 solid-state MAS NMR spectroscopic studies of I and 2 confirm the existence of only one isomer, but reveal disorder phenomena in the solid state within the cyclo-P2S3 middle deck. Addition Of excess W(CO)(5)THF to 1 proceeds via elusive [CP*2MO2P2S3{W(CO)(5)}(2)] to give the cluster [{Cp*2Mo2W(CO)(3)(mu(2),eta(2:2)-ps)- (mu(3),eta(1:1:2)-PS)(mu(3)-S)}{W(CO)(5)}(2)](5). The molecular structure of 5 contains a Mo2WS core with attached PS dumbbells. Contrary to the planar P2S3 central deck in 2 and 3 the PS dumbbells are perpendicular to each other in 5.
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