Paul J. Low

Reactions of M(CCCCR)(CO)3Cp [M=Mo, W; R=H, Fe(CO)2Cp, M(CO)3Cp] with cobalt carbonyls: X-ray structures of {Cp(OC)8Co2M(μ3-C)}CC{(μ3-C)Co2M′(CO)8Cp} (M=M′=Mo, W; M=Mo, M′=W)

Abstract Reactions of Co2(CO)8 with complexes M(CCCCR)(CO)3Cp [M=Mo, W; R=H, Fe(CO)2Cp] are described. Simple adducts containing a Co2(CO)6 group attached to the least sterically-hindered CC triple bond are formed. In contrast, when R=M(CO)3Cp (M=Mo, W), bis-cluster complexes {Cp(OC)8Co2M(μ3-C)}CC{(μ3-C)Co2M′(CO)8Cp} (M=M′=Mo, W; M=Mo, M′=W) were obtained. All three complexes were structurally characterised. Important features are the presence of both distal and proximal Cp groups in each molecule, and the formal oxidation of the –CC–CC– chain in the precursor to C–CC–C system in the products. Extended Huckel and Density Functional Theory calculations have been used to rationalise the observed structures of the M3C4M3 complexes. The reaction between Co2(μ-dppm)(CO)6 and {W(CO)3Cp}2(μ-C4) gave the simple adduct Co2(μ-dppm){μ-[Cp(OC)3W]C2CC[W(CO)3Cp]}(CO)4.

Heterometallic complexes containing C4 chains. X-ray structures of {Cp(OC)3W}CCCC{Ir(CO)(PPh3)2(O2)} and cis-Pt{CCCC[W(CO)3Cp]}2(PEt3)2

Abstract Heterometallic diyndiyl complexes containing tungsten linked to metals of Groups 6–12 through a C 4 bridge are readily prepared from simple derivatisation reactions of the complex W(CCCCH)(CO) 3 Cp bearing the parent diynyl ligand. Complexes {Cp(OC) 3 W}CCCC{ML n } [ML n =M(CO) x Cp ( n =3, M=Mo, W; n =2, M=Fe, Ru), M(CO)(PPh 3 ) 2 (M=Rh, Ir), Au(PPh 3 )] have been obtained from CuI-catalysed reactions of W(CCCCH)(CO) 3 Cp ( 1 ) with MXL n (X=halide) in NHEt 2 . Similarly, cis -PtCl 2 L 2 (L=PEt 3 ; L 2 =dppe, dppp) afforded cis -Pt{CCCC[W(CO) 3 Cp]} 2 L 2 . Lithiation of 1 (LiNPr i 2 ), followed by coupling with MnI(CO) 5 , gave {Cp(OC) 3 W}CCCC{Mn(CO) 5 }, while direct reaction of 1 with Hg(OAc) 2 gave Hg{CCCC[W(CO) 3 Cp]} 2 . The Rh and Ir complexes react readily with O 2 at the Group 9 metal centre; the crystal structures of {Cp(OC) 3 W}CCCC{Ir(CO)(PPh 3 ) 2 (O 2 )} and cis -Pt{CCCC[W(CO) 3 Cp]} 2 (PEt 3 ) 2 are reported.

Some ruthenium complexes derived from 1,4-diethynylbenzene: molecular structure of Ru{η3-C[C(CN)2]C(C6H4CCH-4)C(CN)2}(PPh3)Cp

Abstract Reactions of Ru(CCC 6 H 4 CCR-4)(PPh 3 ) 2 Cp [R=SiMe 3 ( 1 ), H ( 3 )] are described. With Co 2 (CO) 8 reactions occur at the CC triple bond furthest from the ruthenium centre; in contrast, tetracyanoethene gave Ru{η 3 -C[C(CN) 2 ]C(C 6 H 4 CCR-4)C(CN) 2 }(PPh 3 )Cp (R=SiMe 3 , H), the molecular structure of the latter being determined. Protonation or methylation of 3 occurs at C β to give the expected vinylidene complexes. With 3 , metallation (LiBu), Sonogashira and oxidative coupling reactions were demonstrated. Coupling with appropriate metal substrates gave a variety of complexes containing RuCCC 6 H 4 CCM (M=W, Rh, Ir, Pt, Au, Hg) moieties.

Some reactions of the ruthenium allenylidene complex [Ru(CCCPh2)(PPh3)2Cp][PF6] with nucleophiles

Abstract Reactions between [Ru(CCCPh 2 )(PPh 3 ) 2 Cp][PF 6 ] and nucleophilic reagents LiMe, NaOMe, KCN and KC 5 H 5 have given the neutral substituted alkynyl–ruthenium complexes Ru{CCCPh 2 (Nu)}(PPh 3 ) 2 Cp. The molecular structures of complexes with Nu=OMe, CN and C 5 H 5 have been determined.

Expeditious synthesis of Re3(μ-H)3(CO)11(NCMe)

Abstract The cluster hydride Re 3 (μ-H) 3 (CO) 11 (NCMe) can be prepared in ca. 90% isolated yield by passing hydrogen into a toluene solution of Re 2 (CO) 8 (NCMe) 2 at 80°C.

Syntheses of complexes containing substituted 4-ethynylquinolines or 1-azabuta-1,3-dienes by addition of imines to a cationic butatrienylidene-ruthenium complex

Abstract Reactions of [Ru(CCCCH 2 )(PR 3 ) 2 Cp] + (R=Ph or OMe) with arylimines ArNCH(C 6 H 4 R) afford either substituted quinolines, Ru{CCC 9 H 4 RN(Ar)}(PR 3 ) 2 Cp, by attack of the terminal carbon of the butatrienylidene ligand at the imine carbon, followed by CC bond formation between the ortho carbon of the N -aryl group and C γ of the unsaturated carbene, or 1-azabuta-1,3-dienyl complexes, formed by cycloaddition of the NCH group to C γ C δ of the carbene, followed by opening of the resulting four-membered ring. Some product dependence on the nature of the substituents in the N - and C -aryl groups is found. The N atoms in the products are strongly basic, being readily protonated, methylated or aurated. The molecular structures of nine complexes are reported, together with that of a new modification of RuCl{P(OMe) 3 } 2 Cp.

Some chemistry of Re2( μ-H) ( μ-C2Ph) (CO)8: X-ray structures of Re2( μ-H) ( μ-C2Ph) (CO)6(PMe3)2, Re2{μ-Au(PPh3)}( μ-C2Ph) (CO)8,Re2 ( μ-X) (μ-dppm) ( μ-C2Ph) (CO)6 [X = H, Br and Au(PPh3)] and Re2( μ-Br)2( μ-dppm) (CO)6

Abstract Reactions of Re 2 (μ-H)(μ-C 2 Ph)(CO),(NCMe) ( 2 ) with 1,8-diazabicyclo[5.4.0]undec-l-ene (dbu), CN t Bu or PMe 3 have given Re 2 (μ-H)(μ-C 2 Ph)(CO) 8− n (L) n [L = dbu, n = l ; L = CN t Bu ( 4 ) or PMe 3 , n = 2]; with dppm, Re 2 (μ-H)(μ-dppm)(μ-C 2 Ph)(CO) 6 ( 6 ) was obtained. Halogenation of 6 has given Re 2 (μ-X)(μ-dppm)(μ-C 2 Ph)(CO) 6 [X = I, Br ( 8 )] and Re 2 (μ-Br) 2 (μ-dppm)(CO) 6 ( 9 ). Cluster AuRe 2 (μ-C 2 Ph)(CO) 8 (PPh 3 ) ( 10 ) was obtained as a minor product from a reaction between 2 and Na[Co(CO) 4 ]/AuCl(PPh 3 ). Replacement of the H in 6 by Au(PPh 3 ) was achieved by reaction with AuMe(PPh 3 ) to give AuRe 2 (μ-dppm)(μ-C 2 Ph)(CO) 6 (PPh 3 ) ( 11 ); in contrast, treatment of 6 with LiMe, followed by addition of AuCI(PPh 3 ) or [{Au(PPh 3 )} 3 O][BF 4 ], gave Re 2 (μ.-H){(μ-(PPh 2 ) 2 CH[Au(PPh 3 )]}(μ-C 2 Ph)(CO) 6 ( 12 ), in which the μ-dppm ligand has been metallated. With {Rh(μ-Cl)(cod)} 2 , the product contains an Re 2 Rh cluster capped by the CH(PPh 2 ) 2 ligand. The X-ray structures of 4 , 6 and 8–11 are reported.

Rhenium complexes from alkynes. X-Ray crystal structures of Re2(μ-2η1,-C4Ph4) (CO)7 and Re{C,O-CH C[Re(CO)4(NMe3)]C(OMe)O}(CO)4

Abstract The molecular structure of Re 2 (μ-2η 1 ,η 4 -C 4 Ph 4 )(CO) 7 obtained from Re 2 (CO) 8 (NCMe) 2 and C 2 Ph 2 , consists of an Re 2 (CO) 7 unit [ReRe 2.874(1) A] bridged by a 2η 1 ,η 4 -C 4 Ph 4 ligand, as proposed by earlier workers. Methyl propiolate is inserted into the ReRe bond of Re 2 (CO) 9 (NCMe), as shown by the molecular structure of the NMe 3 derivative of the product; the NMe 3 ligand is attached to the non-chelated Re atom [ReN 2.31(1) A].

Syntheses and reactions of some cluster complexes containing C4 ligands with iron, ruthenium and cobalt carbonyls

Some reactions of W(CCCCH)(CO)3Cp with metal cluster carbonyls have been studied. With Ru3(CO)10(NCMe)2 the initial product is Ru3{μ3-HC2CC[W(CO)3Cp]}(μ-CO)(CO)9, which readily transforms into Ru3(μ-H){μ3-C2CC[W(CO)3Cp]}(CO)9. Similar chemistry is found with the dppm analogue: three interconverting isomers of Ru3(μ-H){μ3-C2CC[W(CO)3Cp]}(μ-dppm)(CO)7 can be detected in solution. Reactions of Ru3(μ-H){μ3-C2CC[W(CO)3Cp]}(CO)9 with Ru3(CO)12 afforded {Ru3(μ-H)(CO)9}(μ3-η2∶μ3-η2-C2C2){Ru2W(CO)8Cp}, while Fe2(CO)9 gave an analogous product in which three of the ruthenium sites are partially occupied by a total of one or two iron atoms; with Co2(CO)8 the vinylidene cluster {CoRu2(CO)9}(μ3-η2∶μ3-η2-CCHC2){CoRuW(CO)8Cp} was formed, the cluster-bound hydride transferring to the C4 ligand. The molecular structures of five complexes have been determined by single-crystal X-ray studies. Theoretical calculations have rationalised the tendency for the formation of μ3-η2-C2 fragments in these C4 clusters.

CCDC 1570320: Experimental Crystal Structure Determination

Related Article: Simon Guckel, Josef B. G. Gluyas, Sarah El-Tarhuni, Alexandre N. Sobolev, Mark W. Whiteley, Jean-Francois Halet, Claude Lapinte, Martin Kaupp, Paul J. Low|2018|Organometallics|37|1432|doi:10.1021/acs.organomet.8b00099