Addition reactions and crystal structure of trans-CH3Ir(CO)(PPh3)2

Abstract

The complex trans-Melr(CO) (PPh3)2 readily undergoes addition reactions with a variety of small molecules such as H2, CO, Me02CCH=CHC02Me, Me02CC=CC02Me, 02, CH3I, and H2C(0) to yield well-characterized products. Further reactions of the addition complexes are noted in most cases. The species irons-Melr(CO) (PPh3)2 crystallizes in the centrosymmetric triclinic space group Pi with o = 9.2497 (9)A, b = 9.6080 (11) A, c = 10.4855 (14) A, a = 72.390 (10)°, ß = 88.990 (9)°, y = 69.224 (8)°, V = 826.22 (16) A3, Z = 1, and D(caled) = 1.53 g cm"3 for mol wt 759.9. Diffraction data (Mo Ka, 29 = 4.5-50.0°) were collected with a Syntex P21 automated four-circle diffractometer and refined to RF = 1.8% and R"F = 2.1% for the 2922 independent reflections (none rejected). The molecule lies on a center of symmetry and is disordered with CO and Me ligands occupying square-planar sites rigorously coplanar with the iridium atom. The Ir-P distances are each 2.300 (1) A; estimated IMÜO and Ir-Me distances are ~1.835 and ~2.17 A, respectively.

Reactivity of the Heterobinuclear Phenylacetylide-Bridged A-Frame [RhIr(CO)2(μ-CCPh)(Ph2PCH2PPh2)2][O3SCF3] with Small Molecules

“…Spectral identification of the binding mode of the SO 2 ligand is not straightforward. While the ν SO of 1213, 1174, 1063, and 1042 cm -1 in the IR spectrum are consistent with a bridging SO 2 group, these data are also consistent with terminal, pyramidal SO 2 binding, as seen by the similarity of the SO stretches in 5 with those of the analogous mononuclear complex [Ir(CCPh)(CO)(PPh 3 ) 2 (SO 2 )] (ν SO = 1196, 1181, 1050 cm -1 ) 2b. However, the close similarity of the spectral parameters between 1 and 5 argues for analogous structures; furthermore, the presence of only terminal carbonyls in 5 and the known tendency for SO 2 to bridge two metals suggest the structure shown.…”

“…One series of analogous complexes, in which the chloro ligand is replaced by an anionic organic group, such as an alkyl, aryl, or related group, presents an interesting extension to the chemistry. Not only can the electronic influence of this group give rise to interesting reactivity changes at the metal, 1g, but C−C bond formation is also possible through migratory insertion reactions involving carbon-containing substrates and the anionic, organic ligand …”

Formation and structure of tetracarbonylvanadium half-sandwich complexes: tetracarbonyl (.eta.5-sec-butylmethylcyclopentadienyl)vanadium(I) and meso-[(1,1',2,',2a,2a',8b,8b',8a,8a'-.eta.10)3,3'-biacenaphthylenyl]octacarbonyldivanadium(I)

“…The distance between vanadium and the ring plane (of the Cp unit) amounts to 193 pm which is the same or close to what we have found for CpV(CO)4 and several of its derivatives substituted at the Cp ring and/or in the carbonyl ligand domain. 16 The acenaphthylene ring system is remarkably coplanar throughout, with a deviation for C3 of 20.3 pm (14) In CDCI5, there are two signals (5a and 5b) at +187 and +178 ppm, respectively, relative to C5H5V(CO)4, in the approximate intensity ratio 3/1. (15) Crystal data: triclinic, Pi, o = 718.12 (0.27) pm, b = 751.83 (0.21) pm, c = 1260.04 (0.52) pm, a = 92.85 (0.03)°, ß = 90.02 (0.03)°, y = 99.80 (0.03)°, 2 = 2 (one formula unit), V = 669.51 X 106 (pm)3, p(calcd) = 1.5634 kg/L; µ = 6.92 cm"1.…”

Synthesis, Properties, and Reactions of Monosulfonated Triphenylphosphine (PPh2(m-C6H4SO3K) = TPPMS) Complexes of Iridium(I). Crystal and Molecular Structure of [N(CH2C6H5)(C2H5)3+][PPh2(m-C6H4SO3)-]·H2O

“…1 H NMR (DMSO- d 6 ): δ(CH 3 ) = −0.4 (t, J P - H = 9 Hz). All 31 P and 1 H NMR resonances were consistent with those of the PPh 3 analogue . Anal.…”