159899-10-2

Upstream product

• 201230-82-2 carbon monoxide 
• 17534-15-5 Benzene-1,2-dithiol 
• 203922-72-9 Ru2(μ-benzene-1,2-dithiolate)(CO)6 
• 603-35-0 triphenylphosphine 

Relevant academic research and scientific papers

Facile syntheses, isomeric structures, and chemical reactivity of diruthenium(I) complexes [Ru2(CO)4(MeCN)4L2]X2 (L = MeCN, PPh3, PPh2(allyl), PMe3; X- = PF6-, BF4-). A convenient route to 1,2-diamides and 1,2-dithiolates

Alkylating agents such as Et3O+X- (X- = PF6- or BF4-) readily remove the bridging acetate groups of [Ru2(CO)4(O2CMe)2L2] at ambient temperature to give the versatile complexes [Ru2(CO)4(NCMe)4L2]X2 (L = MeCN (1), PPh3 (2), PPh2(allyl) (3), and PMe3 (4)). The crystal structures of 3 and 4 were determined by X-ray crystallography: [3][BF4]2, a = 20.292(6), b = 17.223(7), c = 15.186(3), β = 113.324(18)°, V = 4873(3) A?3, monoclinic C2/c, Z = 4, refined to R = 0.045, Rw = 0.048, and GOF = 2.27. [4][BF4]2, a = 12.570(4), b = 14.251(5), c = 18.773(6) A?, β = 104.96(3)°, V = 3251(9) A?3, monoclinic P21/n, Z = 4, refined to R = 0.044, Rw = 0.044, and GOF = 1.53. Although 3 adopts a trans-staggered structure, 4 is in a cis-staggered geometry. The high reactivity of 1-4 is demonstrated via the cation-anion annihilation between 22+ and the doubly deprotonated anion, (E-E)2-, to give [Ru2(CO)4-{μ-η2,η 2-(E-E)}(PPh3)2] ((E-E)2- = 1,2-(NH)2C6H42- (7); 2,3-(NH)2C10H62- (8); 1,2-(NH)2-4,5-Cl2C6H22- (9); 1,2-(NH)2-4,5-Me2C6H2 (10); 9,10-(NH)2C14H8 (11); and 1,2-S2C6H42- (12)). The structures of 7-12 were also confirmed by an X-ray single-crystal structure of 12: a = 11.155(1), b = 21.302(2), c = 10.183(2) A?, α = 93.65(1), β = 113.43(1), γ = 101.19(1)°, V = 2151.2(6) A?3, triclinic P1, Z = 2, refined to R = 0.038, Rw = 0.046, and GOF = 2.81. The Ru-Ru distances are 2.8647(11) A? in 3, 2.861(1) A? in 4, and 2.6767(5) A? in 12.

Synthesis and reactivity of hydride-bridged ruthenium dithiolene complexes

Syntheses of two homonuclear hydride complexes, viz. hydride-bridged ruthenium dinuclear complex [Ru(η6-C6Me6)(S2C6H4)RuClH(PPh3)2] (3) and dihydride ruthenium dinuclear complex [Ru(η6-C6Me6)(S2C6H4) RuH2(PPh3)2] (4), have been described. Complex 4 was obtained as a mixture of cis- and trans-dihydride isomers in a 10:1 M ratio, as indicated by the proton ratio in 1H NMR spectra. The dinuclear complex 4 reacted with carbon monoxide for 30 min and 1 day under similar conditions to produce dicarbonyl complex [Ru(η6-C6Me6)(S2C6H4)Ru(CO)2(PPh3)] (5), and tetracarbonyl complex [Ru2(CO)4(PPh3)2(S2C6H4)] (6), respectively. On the other hand, treatment of 4 with carbon dioxide under ambient conditions was found to produce formic acid.

Derivative chemistry of [Ru2(μ-bdt)(CO)6], a binuclear ruthenium(I) carbonyl complex containing a bridging benzene-1,2-dithiolate ligand

The known dithiolate-bridged ruthenium(I) complex [Ru2(μ-bdt)(CO)6] (1) (bdt = benzene-1,2-dithiolate) has been prepared in fair yield (55percent) by the sequential treatment of RuCl3 · nH20 with carbon monoxide, benzene- 1,2-dithiol and zinc in a one-pot reaction. Complex 1 reacts readily with monodentate phosphanes to give, stepwise, the penta- and tetracarbonyl derivatives [Ru2(μ-bdt)(CO)(6-n)(PR3)(n)] (n = 1, 2; R = Ph, Cy, iPr). However, the reaction of 1 with one equivalent of bis(diphenylphosphanyl)methane (dppm) affords a mixture of complex 1 and the disubstituted derivative [Ru2(μ-bdt)(CO)4(η1-dppm)2], in which the dppm ligands are monodentate. This mixture is subsequently transformed into a polymeric material of formula [{Ru2(μ-bdt)(CO)4}(μ-dppm)](n), which consists of binuclear 9Ru2(μbdt)(CO)4} units linked to each other by bridging dppm ligands. The use of two equivalents of dppm leads to [Ru2(μ- bdt)(CO)4(η1-dppm)2] in quantitative yield. The X-ray diffraction structure of [Ru2(μ-bdt)(CO)4(PiPr3)2] (3c) confirms that the phosphane ligands are located in axial positions, cis to both sulfur atoms, and that the Ru-Ru distance is short [2.6753(7) A?]. A comparative study of the reactivity of complexes 1 and 3c with the electrophiles H+, [Au(PPh3)]+, and HgCl2 has allowed the isolation of the derivatives [Ru2(μH)(μ- bdt)(CO)(6-n(PiPr3)(n)][BF4] (n = 0, 2), [Ru2Au(μ-bdt)(CO)(6- n)(PiPr3)(n)(PPh3)][BF4] (n = 0, 2) and [Ru2HgCl2(μ-bdt)(CO)(6- n)(PiPr3)(n)] (n = 0, 2), respectively.