“…This is the case, for example, of the multiply bonded complexes [Mn 2 (μ-H) 2 (CO) 6 (μ-tedip)] and [M 2 Cp 2 (CO) 4 ] , or the intermediate species generated through thermal or photochemical treatment of suitable electron precise substrates . There are also examples of this kind of addition to highly coordinatively unsaturated d 10 metal fragments . The remarkable aspect of the process leading to compounds 4 is that cations [M 2 Cp 2 (CO) 2 L(μ-dppm)] 2+ have a rather high electron deficiency and are then not very well suited for inducing oxidative addition reactions.…”
Reaction of the unsaturated tricarbonyl complex [W 2 Cp 2 (µ-CO)(CO) 2 (µ-dppm)](BAr′ 4 ) 2 with HSPh leads to the thiolate-bridged complex [W 2 Cp 2 (µ-SPh)(µ-CO)(CO) 2 (µ-dppm)](BAr′ 4 ), which is obtained as a mixture of two isomers. This reaction proceeds faster in the presence of a base (1,8-diazabicyclo[5.4.0]undec-7-ene, DBU), as expected. The title compound also reacts at room temperature with stoichiometric amounts of phosphines HPRwhich display a trans relative geometry of their phosphide and diphosphine ligands. Deprotonation of these hydride complexes with DBU gives the cis phosphide compounds [W 2 Cp 2 (µ-PR 1 R 2 )(CO) 2 (µ-dppm)](BAr′ 4 ), through an unexpected reduction and dehydrogenation/isomerization pathway. This overall deprotonation process is not reversible, and treatment of the latter compound with HBF 4 ‚OEt 2 gives the hydride isomer cis-[W 2 Cp 2 (µ-H)(µ-PR 1 R 2 )(CO) 2 (µ-dppm)](BAr′ 4 )(BF 4 ), which displays a strong hydrogen bond interaction between the bridging hydride ligand and the external BF 4anion. Treatment of the title compound with N 2 CHSiMe 3 or HCtC(p-tol) leads to dicarbonyls [W 2 -Cp 2 {µ-κ 1 -N 2 CH(SiMe 3 )}(CO) 2 (µ-dppm)](BAr′ 4 ) 2 or [W 2 Cp 2 {µ-η 2 :η 2 -HCC(p-tol)}(CO) 2 (µ-dppm)]-(BAr′ 4 ) 2 (two isomers), displaying four-electron-donor diazoalkane or alkyne bridging ligands.
“…This is the case, for example, of the multiply bonded complexes [Mn 2 (μ-H) 2 (CO) 6 (μ-tedip)] and [M 2 Cp 2 (CO) 4 ] , or the intermediate species generated through thermal or photochemical treatment of suitable electron precise substrates . There are also examples of this kind of addition to highly coordinatively unsaturated d 10 metal fragments . The remarkable aspect of the process leading to compounds 4 is that cations [M 2 Cp 2 (CO) 2 L(μ-dppm)] 2+ have a rather high electron deficiency and are then not very well suited for inducing oxidative addition reactions.…”
Reaction of the unsaturated tricarbonyl complex [W 2 Cp 2 (µ-CO)(CO) 2 (µ-dppm)](BAr′ 4 ) 2 with HSPh leads to the thiolate-bridged complex [W 2 Cp 2 (µ-SPh)(µ-CO)(CO) 2 (µ-dppm)](BAr′ 4 ), which is obtained as a mixture of two isomers. This reaction proceeds faster in the presence of a base (1,8-diazabicyclo[5.4.0]undec-7-ene, DBU), as expected. The title compound also reacts at room temperature with stoichiometric amounts of phosphines HPRwhich display a trans relative geometry of their phosphide and diphosphine ligands. Deprotonation of these hydride complexes with DBU gives the cis phosphide compounds [W 2 Cp 2 (µ-PR 1 R 2 )(CO) 2 (µ-dppm)](BAr′ 4 ), through an unexpected reduction and dehydrogenation/isomerization pathway. This overall deprotonation process is not reversible, and treatment of the latter compound with HBF 4 ‚OEt 2 gives the hydride isomer cis-[W 2 Cp 2 (µ-H)(µ-PR 1 R 2 )(CO) 2 (µ-dppm)](BAr′ 4 )(BF 4 ), which displays a strong hydrogen bond interaction between the bridging hydride ligand and the external BF 4anion. Treatment of the title compound with N 2 CHSiMe 3 or HCtC(p-tol) leads to dicarbonyls [W 2 -Cp 2 {µ-κ 1 -N 2 CH(SiMe 3 )}(CO) 2 (µ-dppm)](BAr′ 4 ) 2 or [W 2 Cp 2 {µ-η 2 :η 2 -HCC(p-tol)}(CO) 2 (µ-dppm)]-(BAr′ 4 ) 2 (two isomers), displaying four-electron-donor diazoalkane or alkyne bridging ligands.
“…The stirred solutions were electrolyzed at the appropriate potential until a color change was observed. RuCp(Ph 3 P)(CO)Cl, RuCp(Ph 3 P)(η 1 -dppm)Cl, Pt(COD)Cl 2 , Pt(PhCN) 2 Cl 2 , Mo(CO) 3 (μ-dppm) 2 Pt(H)Cl, and MoCp(CO) 2 (μ-PPh 2 )(μ-H)Pt(PPh 3 )Cl were prepared by literature methods. Ru 3 (CO) 12 , K 2 PtCl 4 , PtCl 2 , and RuCl 3 · x H 2 O were obtained from Johnson Matthey and used as received.…”
As starting materials for heterobimetallic complexes, [RuCp(PPh(3))CO(PPh(2)H)]PF(6) and [RuCp(PPh(3))CO(eta(1)-dppm)]PF(6) were prepared from RuCp(PPh(3))(CO)Cl. In the course of preparing [RuCp(eta(2)-dppm)(eta(1)-dppm)]Cl from RuCp(Ph(3)P)(eta(1)-dppm)Cl, the new monomer RuCpCl(eta(1)-dppm)(2) was isolated. The uncommon coordination mode of the two monodentate bis(phosphines) was confirmed by X-ray crystallography [a = 11.490(1) Å, b = 14.869(2) Å, c = 15.447(2) Å, alpha = 84.63(1) degrees, beta = 70.55(1) degrees, gamma = 72.92(1) degrees, V = 2378.7(5) Å(3), d(calc) = 1.355 g cm(-)(3) (298 K), triclinic, P&onemacr;, Z = 2]. The dppm-bridged bimetallic complexes RuCp(PPh(3))Cl(&mgr;-dppm)PtCl(2), RuCpCl(&mgr;-dppm)(2)PtCl(2), and [RuCp(PPh(3))CO(&mgr;-dppm)PtCl(2)]PF(6) each exhibit electrochemistry consistent with varying degrees of metal-metal interaction. The cationic heterobimetallic complexes [Mo(CO)(3)(&mgr;-dppm)(2)Pt(H)]PF(6) and [MoCp(CO)(2)(&mgr;-PPh(2))(&mgr;-H)Pt(PPh(3))(MeCN)]PF(6) were prepared by chloride abstraction from the corresponding neutral bimetallic species and show electrochemical behavior similar to the analogous Ru/Pt complexes.
“…20% in CD 2 Cl 2 solution. A similar procedure has been used to prepare [(OC) 5 Mo(μ-PPhH)PtCl(PEt 3 ) 2 ] and [{(OC) 5 Mo(μ-PPhH)} 2 Pt(PEt 3 ) 2 ] (the X-ray crystal structures of which have been determined) and has been extended to a number of other molybdenum and tungsten secondary phosphine complexes (see Table ). − 15 Crystal structure of [(OC) 4 Cr(μ-PPh 2 )(μ-CO)Pt(η 3 -cyclooctenyl)]. Reprinted from ref .…”
Section: Phosphido-bridged Compoundsmentioning
confidence: 99%
“…100 The (the X-ray crystal structures of which have been determined) 102 and has been extended to a number of other molybdenum and tungsten secondary phosphine complexes (see Table 6). [103][104][105]…”
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