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• 108417-91-0 W(CH₃)(CO)2(NO)(P(C₆H₅)3)2 

Relevant academic research and scientific papers

Syntheses and reactions of WH(CO)2(NO)(P(C6H5)3)2 and related tungsten nitrosyl complexes

cis-W(CO)4(PPh3)2 (1c) or trans-W(CO)4(PR3)2 (1t) (R = C6H5, p-CH3C6H4) reacted with NOPF6 in methylene chloride to give cis,mer-[W(CO)3(NO)(PR3)2][PF6] (2-PF6); BF4- and ClO4- salts (2-BF4; 2-ClO4) were also prepared. Halide anions (X = Cl-, Br-, I-) reacted with 2 first to give mer-WX(CO)3(NO)(PPh3) (7a, X = Cl; 7b, X = Br; 7c, X = I) and PPh3, then cis,cis-WX(CO)2(NO)(PPh3)2 (6a, X = Cl; 6b, X = Br; 6c, X = I), and finally trans,trans-WX(CO)2(NO)(PPh3)2 (3a, X = F; 3b, X = Cl; 3c, X = Br; 3d, X = I). Further reaction of 3c with NOPF6 and n-Bu4NX gave WXBr(NO)2(PPh3)2 (4c, X = Br; 4f, X = F). Upon reaction with NO+, trans-Cr(CO)4(PPh3)2 gave good yields of trans-[Cr(CO)4(PPh3)2][PF6] (5), but trans-Mo(CO)4(PPh3)2 produced complex mixtures. Acetate reacted with 2 to form trans,trans-W(η1-CH3CO2)(CO) 2(NO)(PPh3)2 (8) and then trans-W(η2-CH3CO2)(CO)(NO)(PPh 3)2 (11) and CO. Dimethyldithiocarbamate reacted with 2 to form cis-W-(η2-S2CNMe2)(CO) 2(NO)(PPh3) (13) and PPh3 and then trans-W(η2-S2CNMe2)(CO)(NO)(PPh 3)2 (14). In the presence of LiBH4 and PPh3 in tetrahydrofuran, both 3c and 2 were transformed into the tungsten(0) hydride trans,trans-WH(CO)2-(NO)(PPh3)2 (15). This hydride underwent α-insertion reactions with RN3 and RN2+, forming trans-W(η2-RN3H)(CO)-(NO)(PPh3)2 (19a, R = Ph; 19b, R = To) and trans,trans-[W(RN2H)(CO)2(NO)(PPh3) 2]+ (23, R = Ph; 24, R = To), and it underwent β-insertion reactions with RNCNR, CO2, and CS2, forming trans-W(η2-RNCHNR)(CO)(NO)(PPh3)2 (21, R = To), trans,trans-W(η1-HCO2)(CO)2(NO)(PPh 3)2 (9), and trans,trans-W(η1-HCS2)(CO)2(NO)(PPh 3)2 (22). Heating the hydride with RN=NNHR and RN=CHNHR produced trans-W(η2-RN3R)(CO)(NO)(PPh3)2 (20) and 21, respectively. When allowed to react with acids (HX; X = Cl, Br, I, CH3CO2, HCO2, OClO3), 15 gave trans,trans-WX(CO)2(NO)(PPh3)2 (3b, 3c, 3d, 8, 9, 16 (X = OClO3)). The perchlorato ligand in 16 was rapidly displaced by halide and pseudohalide anions but not by CO even at 1000 psi (20-80°C).

Synthesis and reactivity of a neutral tungsten(0) alkyl complex. Insertion of CO2 into the W-CH3 bond of trans,trans-W(CH3)(CO)2(NO)(PPh3)2 and the structural characterization of trans-W(η2-O2CCH3)(CO)(NO)(PPh 3)2

Reaction of trans,trans-WCl(CO)2(NO) (PPh3)2 (1) with CH3Li or (CH3)2Zn affords trans,trans-W-(CH3)(CO)2(NO)(PPH3)2 (2) in good yields. Treatment of 2 with DCl gives 1 and CH3D quantitatively. Reaction of 2 with carbon monoxide (2 atm, 80°C) results in a reversible substitution of CO for PPh3 to give mer-W(CH3)(CO)3(NO)(PPh3) (3). Carbon dioxide undergoes a 1,2-insertion reaction with 2 to give the monodentate acetate complex trans,trans-W[η1-OC(O)CH3](CO) 2(NO)(PPh3)2 (4), which reversibly loses CO on heating to yield the bidentate acetate derivative trans-W(η2-O2CCH3)(CO)(NO)(PPh 3)2 (5). Monoclinie prisms of 5 were grown from a dichloromethane/benzene solution and crystallized in space group P21L/a with Z = 4, a = 20.864 (5) A?, b = 9.729 (2) A?, c = 17.504 (4) A?, and β = 103.21 (1)°. An X-ray diffraction study at -91 ± 3°C showed that the acetate ligand is bound in an asymmetric fashion to the tungsten center and that the nitrosyl and carbonyl ligands are not substantially disordered. Salient metrical parameters of the structure include the following: W(1)-O(4) = 2.249 (5) A?, W(1)-O(5) = 2.217 (5) A?, O(4)-C(6) = 1.270 (10) A?, O(5)-C(6) = 1.302 (10) A?, W(1)-C(8) = 1.914 (8) A?, C(8)-O(9) = 1.171 (9) A?, W(1)-N(10) = 1.836 (7) A?, N(10)-O(11) = 1.203 (9) A?, and W(1)-N(10)-O(11) = 178.3 (6)°. The least-squares refinement converged to R(F) = 0.036 and RW(F) = 0.036 for 3518 unique data with F > 3σ(F).