Structural studies of organomolybdenum complexes containing indium

Abstract

The reaction between InCl3 and 3 equiv of Na[Mo(CO)3(7j-C5H5)] affords the trimolybdenum-indium complex [In¡Mo(CO)3-( -05 5•))3] (2), the structure of which was established by X-ray crystallography. Compound 2 crystallizes in the monoclinic space group P2\/n with a = 11.463 (1) A,b = 17.854 (1) A, c = 13.572 (1) ,ß= 101.846 (8)°, and Z = 4. The structure comprises a central trigonal-planar indium atom bonded to three Mo(CO)3(t7-C5H5) fragments via In-Mo bonds. The corresponding reaction between InCl3 and 2 equiv of Na[Mo(CO)3(i7-C5H5)] affords the anionic dimolvbdenum complex [InCl2(Mo(CO)3(tj-C5H5)(2]•, which was also characterized by X-ray crystallography. It crystallizes as the sodium salt, THF solvate [Na(THF)2] [InCl2|Mo-(CO)3(t/-C5H5))2] (6) in the triclinic space group P\ with a = 10.750 (2) A, b = 12.457 (2) Á, c = 13.609 (2) A, a = 108.569 (7) °, ß = 95.829 (7)°, and y = 112.248 (6)°a nd contains dimeric units linked by Cl-Na-Cl bridges, each sodium atom being ligated by three chlorines, two THF molecules, and the oxygen of one of the molybdenum-bound carbonyls; Z = 1 dimer per unit cell. Reaction between InCl3 and 1 equiv of [ ( )3( -5 5)] also affords an anionic complex, [InCl3{Mo(CO)3(t;-C5H5)|]", characterized by X-ray crystallography. It crystallizes as the sodium salt, THF solvate [Na(THF)2] [InCl3|Mo(CO)3(7)-C5H5)|] (8) in the monoclinic space group P2{/c with a = 10.160 (1) Á, b = 21.116 (2) Á, c = 11.862 (1) A, and ß = 109.304 (7)°a nd also comprises dimeric units linked by Cl-Na-Cl bridges; Z = 2 dimers per cell. The tungsten analogues of the above three complexes were also prepared and characterized by spectroscopic means. Details of the solution-state properties of all compounds as determined by infrared spectroscopy are discussed.

BH Bond Activation of Trimethylphosphineborane by Transition Metal Complexes: Synthesis of Metal Complexes Bearing Nonsubstituted Boryl−Trimethylphosphine, Cp*M(CO)3(BH2·PMe3) (M = Mo, W)

“…Smith et al have reported the reaction of GaMe 3 with CpW(CO) 3 H, which results in multiple activation of the Ga−C bonds to afford CpW(CO) 3 GaMe 2 , [CpW(CO) 3 ] 2 (μ 2 -GaMe), and [CpW(CO) 3 ] 3 (μ 3 -Ga) besides CH 4 . In the reaction of CpM(CO) 3 H (M = Mo, W) with InMe 3 , μ 3 -indium complexes [CpM(CO) 3 ] 3 (μ 3 -In) are produced exclusively . We also reported that irradiation of CpFe(CO) 2 SiMe 3 in the presence of RSiH 3 (R = t -Bu, CMe 2 CMe 2 H) gave silylene-bridged diiron complexes Cp 2 Fe 2 (CO) 3 (μ-SiHR) .…”

Synthetic and structural studies on Group 13 complexes containing the M(CO)3(η-C5H5) fragment (M = Cr or Mo). Part 2. Complexes [InClx{M(CO)3(η-C5H5)}2]n–(x= 1, n= o; x= 2, n= 1)

“…In ref. 2 we reported the reaction between InCl, and 2 equivalents of Na[M(CO),(q-C,H,)] (M = Mo or W) which afforded the anionic dichloro complexes [InCl, { M(CO),(q-C5Hs)}2]-(M = Mo, 1; or W, 2). Compound 1 was characterised by X-ray crystallography as [Na(thf),]-[InCI,{ Mo(CO),(q-C,H,)},] (hereafter la).…”

“…In ref. 2 we reported details of the reactions between InCl, and equivalent of either Na[ Mo(CO),(q-C5H ,)I or Na[ W(CO),( q-C5H5)] which afforded the anionic complexes [InCl,{ M- (q-C5H5))] can be made directly from the reaction between [MX(CO),(q-C5H5)] and InX. We carried out two similar reactions, viz.…”

“…These are best measured by the torsion angles defined as C1,Cl midpoint-In-Mo-C,H, ring centroid. For 17 this angle is 129.5' for both In-Mo bonds since the molecule lies on a crystallographic C , axis whilst for l a the values are -23.1 for Mo(1) and 98.2" for Mo (2). Clearly the differences between 17 and la are likely to arise as a result of having different cations and therefore corresponding differences in steric and crystalpacking forces.…”

Reactions of Elemental Indium and Indium(I) Bromide with Nickel−Bromine Bonds: Structure of (η5-C5H5)(Ph3P)NiInBr2(OPPh3)

“…Transition metal indium compounds have been studied in the past starting with W. Hieber's early work on In[Co(CO) 4 ] 3 in 1942 up to the present with N. C. Norman's contributions, namely, on group-6 indium complexes, e.g., [(η 5 -C 5 H 5 )(CO) 3 M] n InX 3 - n (L) (M = Cr, Mo, W; n = 2, 3; L = THF, py or other Lewis donors). − Almost all known systems of the type (L m M) n InX 3 - n , which can be viewed as derivatives of trimethylindium or indiumtrihalides, exhibit carbonyl transition metal fragments. Rather few compounds exist which do not carry carbonyl ligands at the transition metal center, only two of which have been structurally characterized: mer -{[(CH 3 ) 3 P] 3 (H)(C 2 H 5 )Ir−In(C 2 H 5 ) 2 } and cis -{(Cy 2 PCH 2 CH 2 PCy 2 )[(CH 3 ) 3 SiCH 2 ]Pt−In[CH 2 Si(CH 3 ) 3 ] 2 } (Cy = cyclo-C 6 H 11 ) …”