Robert A. Head

Some 2,7-dimethylocta-2,6-diene-1,8-diylruthenium phosphine, fluorophosphine and carbonyl complexes

Abstract Dichloro(2,7-dimethylocta-2,6-diene-1,8-diyl)ruthenium(IV), [RuCl2C10H16]2, reacts with carbon monoxide or phosphines to afford air stable complexes of the type RuCl2C10H16·L [L = CO, PF3, PPh3, Me2NPF2, CF3PCl2, and P(OCH2)3CPh]. The 1H and 19F NMR spectra of these compounds are presented and discussed. In RuCl2Cl10H16(Me2NPF2) the two fluorine atoms are magnetically non-equivalent. RuCl2C10H16·PF3 reacts with excess PF3, and subsequent addition of PPh3 affords the ruthenium(II) complex cis-RuCl2(PF3)2(PPh3)2.

Synthesis and reactivity of platinum–formaldehyde complexes [Pt (PR3)2(CH2O)]

Sodium dihydronaphthylide reduction of [PtCl2(PR3)2](R3= Et3, Pri3, Ph3, Et2Ph, or ½Ph2PCH2CH2PPh2) under an ethylene atmosphere gives [Pt(PR3)2(C2H4)] in quantitative yield as shown by 31P n.m.r. spectroscopy. Reactions of the ethylene complexes with CO, CH2I2,(CF3)2CO, (CO2Et)2CO, and CH2O are described. Monomeric formaldehyde reacts to give the first platinum–formaldehyde complexes, [Pt(PR3)2(CH2O)], decomposition of which produces [Pt3(CO)3(PR3)n](n= 3 or 4) and a complex tentatively assigned as [{PtH(PR3)2}2{C(O)OCH2}].

He(I) Photoelectron spectra of mixed carbonyltrifluorophosphine complexes of zerovalent iron

Abstract The UV PE spectra of complexes of the type Fe(CO) x (PF 3 ) 5− x are presented and discussed.

UV photoelectron spectra of first-row transition metal hydridocarbonyl and hydridotrifluorophosphine complexes

Abstract The He(I) photoelectron spectrum of FeH 2 (PF 3 ) 4 is reported, and the bands are assigned and compared with those of the analogous carbonyl complex. Molecular obrital energies for the M H σ-bonding orbitals, metal-3 d orbitals and metal-phosphorus σ-bonding orbitals for the hydridocarbonyl and hydridotrifluorophosphine complexes MnHL 5 , FeH 2 L 4 and CoHL 4 (L CO and PF 3 ) are compared and correlations discussed.

ω-Diazobutanol complexes from the reaction of tetrahydrofuran with bis(dinitrogen) complexes of molybdenum and tungsten: X-ray crystal structure of [MBr{N–NCH(CH2)3OH}(Ph2PCH2PPH2)]+[PF6]–

A complex derived from the reaction of tetrahydrofuran with bis-[1,2-bis(diphenylphosphino)ethane]-bis(dinitrogen)tungsten, and previously formulated as a tetrahydropyridazine derivative, has been shown by X-ray structural analysis to be bis-[1,2-bis(diphenyl-phosphino)ethane]bromo-(ω-diazobutanol-N2)tungsten hexafluorophosphate.

Diazoalkane complexes of tungsten. Crystal structures of [WBr(N–NCHCH2CH2CH2OH)(dppe)2][PF6]·0.5EtOH (1) and [WBr(N–NCMe2)(dppe)2]Br·0.5MeOH (2)

The X-ray crystal-structure determinations of the title complexes are described. Crystals of (1) are monoclinic, space group P21/n, with unit-cell dimensions a= 17.43 (1), b= 17.28(1), c= 19.00 (1)A, β= 100.85(2)°, and Z = 4, and the structure has been refined to R= 0.064 based on 4 168 counter reflections. Crystals of (2) are monoclinic, space group P21/c, with a= 11.745(2), b= 22.638(2), c= 21.029(3)A, β= 111.2(2)°, and Z= 4, and the structure has been refined to R= 0.060 based on 6 402 counter reflections. Complex (1) was previously thought to be [WBr([graphic omitted]H2)(dppe)2][PF6][dppe = 1,2-bis(diphenylphosphino)ethane]. Unusual n.m.r parameters and difficulties in the preparation of diazoalkane complexes where both groups are larger than methyl are explained.

Substitution reactions of cis-bis(2,2′-bipyridine)dicarbonyl(solvent)molybdenum(II) and cis-bis(2,2′-bipyridine)dicarbonyltungsten(II) salts with uni-, bi-, and ter-dentate tertiary phosphines, trimethyl phosphite, nitric oxide, and 2,2′-bipyridine

Reaction of cis-[Mo(CO)2(bipy)2(NCMe)][BF4]2(bipy = 2,2′-bipyridine) with PPh3 and PBun3 substitutes the solvent to produce [Mo(CO)2(bipy)2(PR3)][BF4]2(R = Ph or Bun) under mild conditions. Oxidation of cis-[Mo(CO)2(bipy)2] with Ag[BF4] in trimethyl phosphite at room temperature gives [Mo(CO)2(bipy)2{P(OMe)3}][BF4]2. Under similar conditions, further substitution of one carbonyl ligand, to give [Mo(CO)(bipy)2L2][BF4]2[L = PEt3 or P(OMe)3], or both carbonyl ligands to give [Mo(NO)2(bipy)2][BF4]2 or [Mo(bipy)3][BF4]2 may occur. Reaction of cis-[W(CO)2(bipy)2][BF4]2 with the same phosphorus donor ligands results in the substitution of bipy to form cis-[W(CO)2(bipy)L2][BF4]2[L = PPh3 or P(OMe)3]; reaction with bis(diphenylphosphino)methane (dppm) or 1,2-bis(diphenylphosphino)ethane (dppe) produces [WF(CO)2(bipy)(L–L)][BF4](L–L = dppm or dppe). Reaction of [Mo(CO)2(bipy)2(NCMe)][BF4]2 with dppe produces [Mo(CO)(bipy)2(dppe)][BF4]2. With bis(2-diphenylphosphinoethyl)phenylphosphine (bdpp), cis[W(CO)2(bipy)2][BF4]2 forms [W(CO)2(bipy)(bdpp)][BF4]2 in high yield. The new complexes have been characterised by microanalysis, spectroscopy (i.r., 1H, 13C, 19F, 31P n.m.r., electronic absorption), and conductivity measurements. [Mo(NO)2(bipy)2][BF4]2 reacts with Na[S2CNEt2] to give [Mo(NO)2(S2CNEt2)2].

Phosphine induced reductive elimination reactions : Synthesis of ruthenium(O) fluorophosphine complexes

Abstract The zerovalent ruthenium complexes Ru(PF 2 NMe 2 ) 5 ,Ru(PF 2 NC 4 H 8 ) 5 , Ru(PF 3 ) 3 (PPh 3 ) 2 , and Ru(PF 3 ) 4 (PPh 3 ) arereadily obtained by reductive elimination of acetic acid from RuH(CO 2 Me)(PPh 3 ) 3 by treatment with the appropriate fluorophosphine.

Trichloro-bridged heterobimetallic phosphine complexes containing ruthenium(II) and rhodium(III)

The syntheses of a series of trichloro-bridged heterobimetallic phosphine complexes of the type [(Ph3P)(L)-ClRuCl3 RhClL2](L = PMe2Ph, PEt2Ph, PBun3Ph, PBun3, or PPh3) from the mononuclear complexes [RuCl2-(PPh3)3] and [RhCl3L3] or [RhCl3(PF3)(PPh3)2] are described. The structures of these complexes have been elucidated by 31P n m r. spectroscopy, and the reactions are shown to involve phosphine-ligand transfer from rhodium to ruthenium.

Photoelectron spectroscopic study of metal trifluorophosphine and hydridotrifluorophosphine complexes

Photoelectron spectra of the complexes [M(PF3)6](M = Cr, Mo, and W), [M(PF3)5](M = Fe and Ru), [HM(PF3)4](M = Co,Rh, and Ir), and [HMn(PF3)5] are presented. Spectra are assigned by analogy with those of PF3 and the corresponding metal carbonyl complexes. It is concluded that: (i) PF3 has a greater overall electron-withdrawing effect than CO; (ii)d-orbital ionisation potentials generally increase across a series and down a vertical group; (iii) metal–phosphorus σ bonding increases across a series and down a vertical group; and (iv) the degree of π bonding is not readily ascertained from the p.e. spectra.