Studies of the reactivity of binary thio- and tertiary oxothiomolybdates toward electrophiles. Reactions with dicarbomethoxyacetylene and the synthesis and structures of the [Et4N2[MoO(L)2], anti-[Et4N]2[Mo2O2S2(L)2]], syn-[Ph4P]2[Mo2O2S2(L)2].cntdot.2DMF, Ph4P]2[Mo(L)3]DMF.cntdot.C6H6, and [Ph4P]2[Mo2S2(L)4]2CH2Cl2 complexes (L = 1,2-dicarbomethoxy-1,2-ethylenedithiolate)

Synthesis, Structure, and Behavior in Solution of the Dawson Thio Derivative [(P2W17O61)2(H4Mo4S4O6)]16–

“…Unfortunately, these did not permit the two isomers to be discriminated energetically. The μ-disulfido-bridged dinuclear molybdenum(V) moiety has been observed for both syn and anti stereochemistries, [33,34] and in the present case, the geometrical data, bond lengths, and angles are compatible with both geometries. The bonding schemes in the syn and anti isomers of the [Mo 2 S 4 ] 2+ core were studied theoretically and calculations using the extended Hückel and Fenske-Hall approaches indicated that the syn isomer is the most stable.…”

Reactivity of tetrathiometalates with alkynes. Synthesis and characterisation of dithiolene complexes of Mo, W, and V by ESMS and XRD

“…In the literature, 1a was already obtained through another strategy of synthesis by D. Coucouvanis. This compound was structurally characterised as two isomers, the anti-(NEt 4 ) 2 [Mo 2 (O) 2 (l-S) 2 (g 2 -S 2 C 2 (CO 2 Me) 2 ) 2 ] and the syn-(PPh 4 ) 2 [Mo 2 (O) 2 (l-S) 2 (g 2 -S 2 C 2 (CO 2 Me) 2 ) 2 ] [22], respectively.…”

“…The molybdenum analogues of 3, 4 and 5 have been described by Coucouvanis et al [22]. To have a better understanding of the phenomena which occurred during the reaction, the reaction was monitored by ESMS spectrometry with and without addition of elemental sulphur.…”

Molybdenum Dithiolene Complexes: Trinuclear Mixed-Valence Complexes and Geometrical Isomers of Dinuclear Complexes

“…1 We have reported some reactions at the sulfur bridge of incomplete cubane-type sulfur/ oxygen-bridged molybdenum complexes with Mo 3 (¯3-S)-(¯-S) 2 (¯-X) (X = O, S) cores (Scheme 1): for example, 2 (a) the reaction of [Mo 3 (¯3-S)(¯-S) 3 (H 2 O) 9 ] 4+ with metals to give cubane-type mixed-metal complexes (M = Fe, Ni, etc. ), (b) the reaction of [Mo 3 (¯3-S)(¯-S) 2 (¯-X)(H 2 O) 9 ] 4+ (X = O, S) with acetylene to give adduct complexes (X = O, S) having two carbon-sulfur bonds, (c) the reaction of [Mo 3 (¯3-S)(¯-S) 3 (dtp) 3 -(CH 3 CN)(¯-OAc)] with methyl propiolate (HC¸CCOOCH 3 , MP) to give cage-type complexes having three carbon-sulfur bonds, (d) the reaction of [Mo 3 (¯3-S)(¯-S) 3 (PPh 3 ) 3 Cl 4 (H 2 O) 2 ] with diphenylacetylene (PhC¸CPh, DPA) to give a photosensitive Mo(V) dinuclear complex, and (e) the reaction of [Mo 3 (¯3-S)(¯-S) 3 (dtp) 3 (CH 3 CN)(¯-OAc)] with dimethyl acetylenedicarboxylate (CH 3 OOCC¸CCOOCH 3 , DMAD) in neat acetone yielded an adduct.…”

“…Photoisomerization was conducted using a Asahi Spectra Max-303 xenon-lamp projector. 1 H NMR spectra were measured on a Bruker ARX-400R spectrometer with acetnitrile-d 3 as solvent and chemical shifts are referenced to the residual proton impurity of the deuterated solvent (1.94 ppm vs. TMS). If necessary, TMS was used as the intensity standard.…”