113288-12-3Relevant academic research and scientific papers
Synthesis and reactions of [(OC)3Fe(μ-dppm)(μ-CO) Pt(PPh3)] with acetylenes or allene: Crystal structures of [(OC) 3Fe(μ-dppm)(μ-CO)Pt(PPh3)], [(OC) ...
Fontaine, Xavier L. R.,Jacobsen, Grant B.,Shaw, Bernard L.,Thornton-Pett, Mark
, p. 662 - 664 (1987)
full title:Synthesis and reactions of [(OC)3Fe(μ-dppm)(μ-CO) Pt(PPh3)] with acetylenes or allene: Crystal structures of [(OC) 3Fe(μ-dppm)(μ-CO)Pt(PPh3)], [(OC) 2Fe(μ-dppm){μ-σ:η3-C(O)C2H 2}Pt(PPh3)], and [(OC)3Fe(μ-dppm){μ- CH2C(=CH2)}Pt(PPh3)] (dppm = Ph 2PCH2PPh2) [(OC)3Fe(μ-dppm)(μ-CO)PtCl2] (dppm = Ph 2PCH2PPh2) is reduced by NaBH4 in the presence of PPh3 to give the electron-rich [(OC) 3Fe(μ-dppm)(μ-CO)Pt(PPh3)], which reacts with acetylene(s) or allene under mild conditions to give the title compounds and is protonated to give a hydride.
Organo-Platinum-Iron Complexes containing One Bridging Ph2PCH2PPh2 Ligand. Crystal Structures of , Pt(PPh3)>, and
Fontaine, Xavier L. R.,Jacobsen, Grant B.,Shaw, Bernard L.,Thornton-Pett, Mark
, p. 741 - 750 (1988)
Treatment of (dppm = Ph2PCH2PPh2) with gave the bimetallic (1) in 75percent isolated yield.Complex (1) was also prepared by the sodium tetrahydroborate reduction of in the presence of PPh3.Its structure was established by X-ray crystallography: the crystals are triclinic, space group P1, with a = 1177.3(2), b = 1198.4(1), c = 1776.5(1) pm, α = 103.34(1), β = 107.81(1), γ = 91.76(1) deg, and Z = 2; final R factor 0.0257 for 5422 observed reflections.The structure shows that one of the carbonyl ligands is almost symmetrically bridging the Fe-Pt bond.Protonation of complex (1) with HBF4.OEt2 gave the hydride (4), 1H n.m.r. studies of which indicated the hydride ligand to be terminal on platinum.Ethyne reacted with (1) at 20 deg C to give the complex Pt(PPh3)> (5), the structure of which was established by X-ray crystallography: the crystals are orthorhombic, space group Pbca, with a = 1898.9(4), b = 1828.3(3), c = 2414.4(5) pm, and Z = 8; r 0.0381 for 4163 observed reflections.The molecule contains a dimetallacyclopentenone ring in which the ethylenic bond is ε2-bound to iron, so that the C(O)C2H2 moiety is ?-co-ordinated to platinum and ε3-co-ordinated to iron.Unsymmetrical alkynes (MeC=CH, PhCCH, 4-MeC6H4CCH, MeNHCH2CCH, HOMe2CCCH, and MeCO2CCH) also reacted with complex (1), at 80 deg C, to give complexes of type Pt(PPh3)>.At 20 deg C, MeCCH and 4-MeC6H4CCH reacted with (1) to give isolable complexes of type Pt(PPh3)> which isomerised in solution, at rates dependent on the steric bulk of R, to complexes of type Pt(PPh3)>.The mechanism of the alkyne-insertion reactions appears to involve an intermediate containing a monodentate dppm ligand co-ordinated to iron, formed by opening of the five-membered FePCPPt ring in (1).Protonation of the alkyne complexes breaks the alkyne-CO link to give μ-vinyl cations of type + (R = H, Me, or C6H4Me-4).The structure of (16) has also been established by X-ray crystallography: the crystals are monoclinic, space group Cc, with a = 2321.3(3), b = 1091.2(2), c = 1962.6(2) pm, β = 98.48(1) deg, and Z = 4, R 0.0460 for 3615 observed reflections.The structure shows that the μ-CMe=CH2 moiety is ?-co-ordinated to platinum and ε2-co-ordinated to iron.Treatment of complex (1) with MeO2CCCCO2Me displaced the PPh3 ligand to give (19).The complex (20) was formed in high yield when SO2 was bubbled through a dichloromethane solution of (1).In addition, analogues of many of the above complexes have been prepared with (Ph2P)2C=CH2.
