Tetracarbonyl Complexes Research Articles

ChemInform Abstract: Synthesis of γ‐Keto Amides (III) via Nucleophilic Attack on Iron Tetracarbonyl Complexes (I) of α,β‐Unsaturated Amides.

ChemInformVolume 20, Issue 45 Heterocyclic Compounds ChemInform Abstract: Synthesis of γ-Keto Amides (III) via Nucleophilic Attack on Iron Tetracarbonyl Complexes (I) of α,β-Unsaturated Amides. A. POUILHES, A. POUILHES Dep. Chem., Univ. Warwick, Coventry CV4 7AL, UKSearch for more papers by this authorS. E. THOMAS, S. E. THOMAS Dep. Chem., Univ. Warwick, Coventry CV4 7AL, UKSearch for more papers by this author A. POUILHES, A. POUILHES Dep. Chem., Univ. Warwick, Coventry CV4 7AL, UKSearch for more papers by this authorS. E. THOMAS, S. E. THOMAS Dep. Chem., Univ. Warwick, Coventry CV4 7AL, UKSearch for more papers by this author First published: November 7, 1989 https://doi.org/10.1002/chin.198945192AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume20, Issue45November 7, 1989 RelatedInformation

Rhodium complexes of the binucleating ligands pyridine-2-thiolate and benzothiazole-2-thiolate. Crystal structures of [{Rh(µ-SC5H4N)(CO)2}2] and [{Rh(µ-SC5H4N)(tfbb)}2]·Me2CO (tfbb = tetrafluorobenzobarrelene)

The binuclear complexes [(Rh)µ-SC5H4N)(diolefin)}2][SC5H4N = pyridine-2thiolate, diolefin = cycle-octa-1,5-diene (cod)(1), norborna-2,5-diene (nbd)(2), or tetrafluorobenzobarrelene (tetrafluorobenzo[5,6] bicyclo[2.2.2]octa-2,5,7-triene)(tfbb)(3)] are prepared by reaction of LiSC5H4N with the appropriate complex [{Rh(µ-Cl)(diolefin)}2] and show fluxional behaviour in solution associated with the bridging ligands. The related compounds [{Rh(µ-C7H4NS2)(diolefin)}2][C7H4NS2= benzothiazole-2-thiolate, diolefin = cod(5), nbd(6), or tfbb(7)] are prepared by a similar route. Carbonylation reactions of (1) and (5) give the tetracarbonyl complexes [{Rh(µ-L)(CO)2}2][L = SC5H4N (4) or C7H4NS2(8) respectively]. Triphenylphosphine replaces carbon monoxide stepwise in compound (4) yielding the mono-(10) and di-substituted (11) complexes whilst the disubstituted complex [{Rh(µ-C7H4NS2)(CO)(PPh3)}2](9) is obtained from compound (8). Methyl iodide adds to complexes (4) and (10) affording respectively the diacetyl complexes [{Rh(µ-SC5H4N)(COMe)I(CO)}2](12) and [{Rh)(µ-SC5H4N)(COMe)l}2(CO)(PPh3)](13). The molecular structures of (3) and (4) have been determined by X-ray analyses. Crystals of (3) are triclinic, space group P, with a= 13.772(7), b= 14.184(8), c= 9.738(4)A, α= 108.99(2), β= 75.65(3), γ= 106.04(3)°, and Z= 2. Crystals of (4) are orthorhombic, space group P21212 (no, 18), with a= 14.637(6), b= 6.734(4), c= 8.852(5)A, and Z= 2. Both complexes are binuclear with two pyridine-2-thiolate groups acting as bridges. In (4) both ligands, having a head-to-tail disposition, bridge the metal centres through the N and S atoms whereas in (3) one of the pyridine-2-thiolate ligands bridges through the S atom only. The square-planar environments of the Rh atoms are completed by two tfbb ligands [(3)] or four CO groups [(4)], with metal–metal separations of 3.028(2) and 2.941 (2)A respectively.

Synthesis of γ-ketoamides via nucleophilic attack on iron tetracarbonyl complexes of α,β-unsaturated amides

Organolithium and Grignard reagents react with the readily-formed iron tetracarbonyl complexes of α,β-unsaturated amides to give γ-ketoamides in good yield via acyl transfer from the metal to the β carbon of the α,β-unsaturated amide.

Rhodium complexes of trisubstituted olefins: Syn selective directed hydrocarboxylation

Use of [di-μ-chloro(diethylene)(dicarbonyl)dirhodium(I)] allows for the formation of bidentate trisubstituted olefinic amine complexes which could not be prepared from the analogous tetracarbonyl complex. These trisubstituted olefin complexes allow for the verification of the syn selectivity in the directed hydrocarboxylation reaction.

Reactivity of heterodiene metal carbonyl complexes

Addition of hard nucleophiles to iron tricarbonyl complexes of α,β-unsaturated ketones and iron tetracarbonyl complexes of α,β-unsaturated esters produces γ-ketocarbonyl compounds. Nucleophilic addition to iron tricarbonyl complexes of α,β-unsaturated imines leads either to pyrrole or α,β-unsaturated amine formation

Synthese und Reaktivität von Dienylmetall-Verbindungen

Abstract C 5 H 5 Mo(CO) 3 I reacts with AgBF 4 in the presence of EMe 2 (E  S, Se, Te) to give the cations [C 5 H 5 Mo(CO) 3 (EMe 2 )] + (I). The dicarbonyl cations [C 5 H 5 Mo(CO) 2 (EMe 2 ) 2 ] + (II) are obtained as mixtures of the cis and trans isomers, the latter predominating, after the oxidation of (C 5 H 5 Mo(CO) 2 ) 2 with [(C 5 H 5 ) 2 Fe]BF 4 in the presence of EMe 2 . [C 5 H 5 Mo(CO) 2 (SMe 2 ) 2 ] + (IIa) dimerises on heating to give the SMe 2 -bridged dication [(C 5 H 5 Mo(CO)(μ-SMe 2 )) 2 ] 2+ (III) whereas attempts to prepare the analogous S(t-C 4 H 9 ) 2 complex lead to the tetracarbonyl complex [(C 5 H 5 Mo(CO) 2 ) 2 (μ-S(t-C 4 H 9 ) 2 )] 2+ (IV).

Synthesis and 1H‐, 13C‐, and 57Fe‐NMR spectra of mono‐ and bis[tricarbonyl(η4‐diene)iron], and (η3‐allyl)tetracarbonyliron trifluoroborate complexes

AbstractA variety of mono‐ and bis[Fe(CO)3(η4‐diene)] complex with alky, CH2OH, CHO, COCH3, COOR, and CN substituents on the 1,3‐diene system have been synthesized. Dienes with a (Z)‐configuration terminal Me group show steric inhibition of metal complexation resulting in lower yields and formation of tetracarbonyl(η2‐diene) and tricarbonyl(η4‐heterodiene) complexes as additional products. Regioselective attack by C‐nucleophiles at the carbonyl C‐atoms of the functional group with or without concomitant 1,3 mogration of the Fe(CO)3 group was used to synthesize polyenes and isoprenoid building blocks as mono‐ or dinucliar Fe(CO)3 complexes. Wittig‐Horner‐type reactions of Fe(co)3‐complexed synthons result in sterospecific formation of (E)‐configurated olefins. The 1H‐, 13C‐ and 57Fe‐NMR spectra of olefinic and allylic organoiron complexes are reported, H,H,C,H, and C,C coupling constants have been evaluated and are analyzed in terms of the geometry of the coordinated diene. The results are corroborated by the crystal structure of tricarbonyl[3–6‐η‐((E)‐6‐methyl‐3,5‐heptadiene‐2‐one)]iron(34) which shows an unusual distortion of the (CH3)2C = group, The 57Fe‐NMR chemical shifts extend over the ranges of 0–600 ppm for [Fe(CO)3(η4‐diene)] complexes, 780–1710 ppm for [Fe(CO)4(η3‐allyl)] [BF4] and [FeX(CO)3(η4‐allyl)] complexes, and 1270–1690 ppm for [Fe(CO)3(η4‐enone)] complexes, relative to Fe(CO)5.

Anionic tetracarbonyl 2-carboxypiridinato or 2-carboxyquinolinato of tungsten(O). reactions with mercury(II) derivatives

New anionic tetracarbonyl complexes, [W(N,O)(CO) 4] −, containing (N,O)-donor ligands (2-picolinate and 2-quinaldinate) have been isolated, and their reactions with HgX 2 (X = Cl, Br, CN) studied. The reactions give either anionic or neutral compounds, containing WHg bonds, of types [W(N,O)(CO) 3(HgX)(X)] − (X = Cl, Br), [W(N,O)(CO) 3(HgBr)] n , [Ph 4P] 2[>W(N,O)(CO) 3} 2(HgX 2)] (X - Cl, CN) and [Ph 4P][W(CN)(N,O)(CO) 2 Hg(CN) 2], depending on the reaction conditions.

Group VI metal tetracarbonyl complexes with 3,6-bis(2′-pyridyl)pyridazine and 7,10-bis(2′-pyridyl)-8,9-diazafluoranthene

In a comparative study, group VI tetracarbonyl complexes with 3,6-bis(2′-pyridyl)pyridazine (dppn) and 7,10-bis(2′-pyridyl)-8,9-diazafluoranthene (dpaf) have been synthesized and characterized by elemental analyses, IR, 1H NMR and electronic spectroscopy. The energy of the first MLCT electronic transition, for each ligand follows the order Mo>W>Cr, and shows that dpaf undergoes the stronger backbonding interaction. Hitherto, no other examples of 7,10-bis(2′-pyridyl)-8,9-diazafluoranthene transition metal complexes have been reported.

Low-temperature photochemistry of matrix-isolated iron tetracarbonyl complexes of .alpha.,.beta.-unsaturated esters. Olefinic carbon vs. ester group coordination

Low-temperature photochemistry of matrix-isolated iron tetracarbonyl complexes of .alpha.,.beta.-unsaturated esters. Olefinic carbon vs. ester group coordination

ChemInform Abstract: Mono‐ and Di‐carbonyl Complexes of Molybdenum(II) with Mixed Bidentate Ligands. X‐Ray Crystal Structure of (MoBr2(CO)(bipy)(Ph2PCH2PPh2)) (bipy: 2,2′‐bipyridine): A Novel Type of (M(bidentate)2(unidentate)3) Structure.

AbstractThe seven‐coordinated dicarbonyl‐Mo complexes (II) with bidentately coordinated NN‐ligands and with only via one P atom coordinated diphosphine are prepared as shown starting from the NN‐ligand tetracarbonyl complexes (I).

Steric influences on sulphur inversion barriers in group 6a tetracarbonyl complexes of dithioethers

The complexes cis-[M(CO)4(RSCH2CH2SR)] (M = Cr, Mo, W, R =t Bu; M = W, R = Me, Et, iPr, tBu) and cis-[M(CO)4(cis-RSCHCHSR)] (M = Cr, Mo, W; R = Me, tBu) have been synthesised, and sulphur inversion studied using variable temperature 1H and 13C {1H} NMR techniques. For complexes of the saturated ligands, signals due to both DL and meso invertomers were observed at −90°C, with the relative populations of these invertomers being dependent on the steric bulk of the alkyl groups attached to sulphur. Sulphur inversion barriers, which have been calculated via total bandshape analysis of the variable temperature NMR spectra of these complexes, show a marked dependence on the steric requirements of the dithioether ligand. For the complexes of the unsaturated ligands, only the meso-invertomers were observed at limiting low temperatures (ca. −90°C), and sulphur inversion barriers were therefore not able to be calculated in these cases.

Four bridging bis chelate ligands with very low lying .pi.* orbitals. MO perturbation calculations, electrochemistry, and spectroscopy of mononuclear and binuclear group 6 metal tetracarbonyl complexes

Four bridging bis chelate ligands with very low lying .pi.* orbitals. MO perturbation calculations, electrochemistry, and spectroscopy of mononuclear and binuclear group 6 metal tetracarbonyl complexes

ChemInform Abstract: Synthesis of a New Type of Metal Dithiolene Complex via an Induced Reaction of Acetylenes with a Ruthenium Sulfide.

AbstractThe air‐stable (p,n2‐S2)(u,n′‐S2) starting Complex (II) is prepared along with Cp 4Ru4S6(yie1d 20%) by oxidation of the tetracarbonyl Complex (I) with S8.

Tri-, bi- and mononuclear rhodium complexes with the anionic polydentate ligands 1,8-naphthyridine-2-one and 5,7-dimethyl-1,8-naphthyridine-2-one

The complexes of the general formula [{Rh(R 2Onapy)(diolefin)} x] (diolefin=cod, tfb, nbd; Onapy =1,8-naphthyridine-2-one) are prepared by reaction of [{RhCl(diolefin)} 2] with HR 2Onapy and potassium hydroxide; complexes with substituted R 2Onapy are mononuclear and those with Onapy are either mono- or binuclear. Both react with carbon monoxide to give [{Rh(μ-R 2Onapy)(CO) 2} 2] (R= H, Me). Reactions of these tetracarbonyl complexes with the species [Rh(CO) 2(Me 2CO) x] + or with [Rh(CO)+(PPh 3) 2(Me 2CO)] ClO 4 give the trinuclear complexes [Rh 3(μ 3-R 2Onapy) 2(CO) 6] ClO 4 and [Rh 3(μ3-R 2Onapy) 2(CO) 4(PPh 3) 2]ClO 4, respectively. The former reacts with diolefins to give the complexes [Rh 3(μ 3-R 2Onapy) 2,(CO) 2(diolefin) 2]ClO 4(diolefin =cod, tfb, nbd). The bi- and trinuclear complexes are deeply-coloured solids which display a strong band in the visible region indicative of intramolecular metal-metal interaction.

ChemInform Abstract: Redox Reactions of Chromium Tetracarbonyl and Tricarbonyl Complexes: Thermodynamic, Kinetic, and Catalytic Aspects of Isomerization in the fac/mer‐Tricarbonyltris(trimethyl phosphite)chromium(l + /0) System

Chemischer InformationsdienstVolume 17, Issue 28 Organoelement Compounds ChemInform Abstract: Redox Reactions of Chromium Tetracarbonyl and Tricarbonyl Complexes: Thermodynamic, Kinetic, and Catalytic Aspects of Isomerization in the fac/mer-Tricarbonyltris(trimethyl phosphite)chromium(l + /0) System A. M. BOND, A. M. BONDSearch for more papers by this authorR. COLTON, R. COLTONSearch for more papers by this authorJ. E. KEVEKORDES, J. E. KEVEKORDESSearch for more papers by this author A. M. BOND, A. M. BONDSearch for more papers by this authorR. COLTON, R. COLTONSearch for more papers by this authorJ. E. KEVEKORDES, J. E. KEVEKORDESSearch for more papers by this author First published: July 15, 1986 https://doi.org/10.1002/chin.198628275AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume17, Issue28July 15, 1986 RelatedInformation

Photochemical hydroformylation catalysis using ruthenium complexes

The catalytic hydroformylation of ethylene and propylene is promoted photochemically by the ruthenium(0) complexes Ru(CO) 3(PPh 3) 2, Ru(CO) 4-(PPh 3) and Ru 3(CO) 12 under UV irradiation at low pressure (ca. 500 torr H 2/CO, 1 1 ) and ambient temperature. Subsequent hydrogenation of the aldehydes is also observed. The photolyses are performed in benzene solution, and result in competitive hydroformylation and hydrogenation of the olefin to yield a product mixture of alkane, aldehydes and alcohols. The use of 13CO shows that the ligands in Ru(CO) 3(PPh 3) 2 exchange readily under photolysis, and that under catalytic conditions Ru(CO) 3(PPh 3) 2 is slowly converted to Ru(CO) 4(PPh 3) as the only observable Ru species in solution. Incorporation of 13C into the carbonyl position of propanal and the C(1) position of 1-propanol is observed directly by NMR spectroscopy. The tetracarbonyl complex exchanges CO readily at ambient temperature, and upon irradiation under H 2 forms the unstable dihydride complex RuH 2(CO) 3(PPh 3). A mechanism is proposed for the observed hydroformylation in which the photochemical step is thought to be generation of a coordinatively unsaturated Ru species.

Redox reactions of chromium tetracarbonyl and tricarbonyl complexes: thermodynamic, kinetic, and catalytic aspects of isomerization in the fac/mer-tricarbonyltris(trimethyl phosphite)chromium(1+/0) system

Etudes electrochimiques sur les melanges de cis- et trans- [Cr(CO) 4 P 2 ] +/0 (P=phosphine tertiaire ou phosphite). Identification des especes trans-[Cr(CO) 4 P 2 ] + . Etude de l'isomerisation de fac-[Cr(CO) 3 (P(OMe) 3 ) 3 ]. Parametres d'activation

Carbonyl complexes of molybdenum and tungsten with sulfur donors: V. Reactions of carbonyl complexes of molybdenum(0) with uninegative (X, Y)-donor ligands (X, Y = S, N, O)

The reactions of the zerovalent carbonyl complexes Mo(CO) 6 and Mo(CO) 4(bipy) with a series of uninegative bidentate (X,Y)-donor ligands (X,Y = xanthates, dithiocarbamates, o-aminophenoxide, o-aminothiophenoxide, 2-picolinate and thioacetate) lead to new anionic tetracarbonyl complex anions [Mo 0(X,Y)(CO) 4] −. These anions, which can be isolated as their tetraphenylphosphonium salts, contain the (X,Y)-ligand as a bidentate group. In the case of (X,Y) = monothioacetate the decarbonylated species [PPh 4][Mo II(TA) 3] is formed. The reacions of the new complexes with allyl bromide and methyl iodide are described.

Phosphinsubstituierte chelatliganden: XVI. Substitution von tetracarbonyl(phosphinothioformimidat)-komplexen des mangans und rheniums mit organophosphor-liganden

The tetracarbonyl(phosphinothioformimidate) complexes (CO) 4 MSC(NR)P Ph 2 (M = Mn: R = Me, Ph; M = Re: R = Me) were treated with a series of organophosphorus ligands, L, to investigate the substitution of octahedral complexes with unsymmetrical P, S-chelate ligands. Where L = PEt 3, MePPh 2, P(OMe) 3 and P(OPh) 3, the facial tricarbonyl complexes 3a, 4a, 7a, 8a, 10a and 12a are obtained as kinetic products which rearrange upon warming into the thermodynamically more stable mer form ( b). The isomerisation is governed more by steric factors than by the π acceptor strength of the ligands L and can be correlated with the Tolman parameter θ. The meridional manganese complexes 1b and 2b are obtained with the bulky ligands, L = PPh 3 and PCy 3, but the facial forms 5a, 6a with L = ClPPh 2 and HPPh 2. Also, the sterically less crowded rhenium complexes 11a (L = PPh 3) and 12a (L = P(OMe) 3) definitely prefer the facial configuration. A disubstituted manganese complex all- cis-(CO) 2L 2 MnSC(NMe)P Ph 2 ( 8c) was formed only with L = P(OMe) 3. The results show that the influence of phosphorus in P, S-chelate ligands on the stereochemical course of the CO substitution dominates.