A new synthetic route to [MF(μ-F)(CO)3]4 (M=Ru, Os) and their reactivity with P(C6H4-4-X)3 (X=OCH3, OH) and P(C6H4-2-OH)3

Synthesis and characterisation of some iridium-carbonyl-fluoride complexes. Crystal structures of [IrF(CO){P(C6H4-2-CH3)3}2] and [IrF2(COD)py2][BF4]

“…We have now found that (1) can be prepared on a large scale (5-10 g) using elemental fluorine as the oxidant for Ir 4 (CO) 12 in HF solution by adapting our previously described procedure for the synthesis of [MF 2 (CO) 3 ] 4 (M = Ru, Os). 22 It is straightforward to monitor the oxidation tensimetrically through the uptake of fluorine gas, since there are no side products generated, and to establish when the reaction is finished since, at room temperature in aHF, (1) is stable to further reaction even under prolonged (weeks) exposure to fluorine gas.…”

“…For the all-trans isomers, the 19 F NMR resonances occur at substantially lower frequencies and the 2 J PF coupling constants are larger than those for the cis-difluoride isomers, as expected for the F-trans-F and F-cis-F arrangements. 13,[21][22][23][24] In the oxidations of the a-diimine complexes, the corresponding iridium(III) difluoride cations are formed as the single F-trans-F isomers, trans-,cis- 2), for which the shifts in d F to low frequency, in comparison to those for the related COD-complexes, mirror those for the related pairs of monodentate phosphine complexes.…”

Alkynylphosphanes as supports for mixed-metal Co4M (M=Ru, Os) fluoride complexes: Syntheses, structures and thermolysis studies

“…Interaction of [MF(l-F)(CO) 3 ] 4 [M = Ru (1a), Os (1b)] [15] with eight equivalents of Ph 2 PC"CPh in tetrahydrofuran at ambient temperature afforded cis,cis,trans-[MF 2 (CO) 2 (Ph 2 PCCPh) 2 ] [M = Ru (2a), Os (2b)] in good yield (Scheme 1). Both complexes have been characterised by IR, 1 H, 19 F and 31 P NMR spectroscopy and gave satisfactory microanalyses (see Table 1 and Section 4).…”

“…Bond lengths (Å ) Ru(1)-F(1) 2.017 (6) 2.017(6) Ru(2)-F (2) 1.989 (6) 1.993(6) Ru(1)-C (1) 1.843 (12) 1.814(12) Ru(1)-C (2) 1.833 (12) 1.840(10) Ru (1) 1.476 (13) 1.483(15) Co(1)-Co (2) 2.4552 (19) 2.461(2) Co(3)-Co (4) 2.454 (2) 2.4519 (19) Bond angles (°) F(1)-Ru (1) (2) 87.18 (18) 86.30(17) P(1)-Ru(1)-P (2) 171.44 (10) 171.55(10) Ru(1)-P(1)-C (15) 113.7(3) 117.1(4) P(1)-C(15)-C (16) 143.0 (8) 146.6(9) C(19)-C(16)-C (15) 142.8 (9) 141.4(11) Ru(1)-P(2)-C (17) 115.3 (4) 113.1(3) P(2)-C(17)-C (18) 146.1 (9) 145.4(8) C(17)-C(18)-C(37) 144.2 (11) 140.6 (9) However, after heating a CDCl 3 solution of ruthenium complex 3a at 50°C for 4 h, both the 31 P and 19 F NMR data supported the formation of a new complex. In the 31 P NMR spectrum, a signal corresponding to the starting material was flanked by a new doublet at d 26.6, while in the 19 F NMR spectrum the additional fluorine signal took the form of a mutually coupled triplet ( 2 J PF 27 Hz) at d À348.4.…”

“…The compounds, (tricarbonyl)rutheniumdifluoride tetramer (1a) [15], (tricarbonyl)osmiumdifluoride tetramer (1b) [15] and phenylethynyldiphenylphosphane [12], were prepared according to previously reported procedures while dicobalt octacarbonyl was obtained from Aldrich Chemical Co. and used without further purification. All other chemicals were obtained commercially and used without further purification.…”