Cymantrene Derivatives Research Articles

Chemistry of vinylidene complexes. 6. Electrochemical reduction and UV spectra of vinylidene derivatives of cymantrene and complexes with an Mn-Pt bond

1. A comparative polarographic study of the phenylvinylidene compounds Cp(CO)2Mn=C= CHPh (I), Cp2(CO)4Mn2(Μ-C=CHPh) (II), and Cp (CO)2MnPt (Μ-CHPh)LL' (III–IX), where L and L′ may be P(OR)3 or CO, has shown that the coordination of the Mn=C bond to a second metal atom results in transposition of the electrophilic center from the α-C atom of the vinylidene group in I to the Mn atoms in II and the Pt atom in III–IX. 2. A correlation between the potential for the electrochemical reduction of the complexes Cp(CO)2MnPt(Μ-C=CHPh)LL' and the energy of the σ → σ* transition of the metal-metal bond in their UV spectra has been established. 3. The attachment of the donor substituents L and L′ to the Pt atoms in compounds III–IX results in an increase in the strength of the Mn-Pt bond. The donor interaction between the Pt atom and the semibridging carbonyl group causes the opposite effect.

Optically active monosubstituted cymantrene derivatives. Relationship of chiroptical characteristics with absolute configuration of the compounds

The results of the study of the chiroptical properties (CD, ORD and [α]), of fourteen optically active monosubstituted cymantrene derivatives with a chiral center directly attached to the Cp ring are summarized for the first time. It has been found that the ( R)-enantiomers of these compounds exhibit a negative Cotton effect for the “metallocenyl” transition in CD spectra within the range 310–360 nm independent on the nature of the substituent and the solvent.

Synthesis and 1H NMR spectra of ferrocene and cymantrene derivatives of divalent ytterbium

The interaction of Yb 0 with (C 5H 5FeC 5H 4) 2Hg and [(OC) 3MnC 5H 4] 2 Hg in THF resulted in the formation of ferrocenyl and cymantrenyl derivatives of divalent ytterbium. Derivatives of the RLnI type may be obtained in low yields from the basis of ferrocene (cymantrenyl) iodides and Yb 0 in THF. The structures of the resulting compounds were characterized by 1H NMR spectra.

Metallocenic thioketones as two-electron ligands.: IV. E–Z isomerization of cymantrene derivatives with an arylcymantrenyl phenyl thioketone ligand

The 1H NMR spectra of binuclear complexes of transition metals with cymantrenyl aryl thioketones have been studied. Temperature-dependence of the 1H NMR spectra of these complexes indicates that the rotation about the C bond is restricted. The energetic parameters for this process have been determined.

Nitrosobenzene as a two-electron ligand in ?-cyclopentadienyl and carbonyl complexes with group VI and VII transition metals

1. Previously unknown derivatives of cymantrene and its rhenium analog [(η5-C5H5)M(CO)2(PhNO)] (M = Mn, Re) with nitrosobenzene as two-electron ligand, and also nitrosobenzene derivatives of group VI B metal carbonyl, were obtained and characterized. 2. All the compounds with PhNO ligands contain phenylnitrene and aniline ions in the mass spectra, the intensity of the latter being maximal. 3. In [W(CO)5(PhNO)], nitrosobenzene is extraordinarily easily reduced to the aniline ligand.

The orientation of substitution in metallation of dimethylaminomethyl-, hydroxymethyl- and diphenylphospino-cymantrenes

Dimethylaminomethyl- and hydroxymethyl-cymantrenes, when treated with n-butyllithium, are selectively metallated in the 2(5) position of the Cp ring and are converted into 1,2-disubstituted derivatives of cymantrene by subsequent treatment with electrophilic reagents. Similar reactions in the case of diphenylphosphinocymantrene result in a selective preparation of 1,3-disubstituted derivatives. The metallation orientation is established by chemical methods and NMR-LIS (lanthanide-induced shift) techniques. A full assignment of signals in the PMR and 13C NMR spectra of the studied monosubstituted cymantrene derivatives has been effected.

Metalloimmunoassay. IV. Manganese‐labelled metallohaptens via cymantrene derivatives

AbstractThe principle of metalloimmunossay (MIA) is briefly described. Results are presented for the synthesis of phenobarbitone metallohaptens incorporating manganese atom labels via functionalized cymantrene derivatives. An atomic absorption calibration curve for the measurement of Mn concentrations with these metallohaptens indicates the feasibility of quantitative detection in the 10−9g. ml−1 range.

Mass spectrometry of π-complexes of transition metals : XX. Dimethylaminoalkyl derivatives of ferrocene and cymantrene; the determination of the distribution and the total content of deuterium label

The mass spectrometry behaviour of dimethylaminomethyl- and α-(dimethylamino)ethyl derivatives of cymantrene and ferrocene, their iodine methylates as well as of the deutero analogues of these compounds has been studied. It has been shown that mass spectrometry can be successfully employed for the quantitative determination of the total deuterium content in aminoalkyl derivatives of cymantrene and ferrocene, the distribution of the label between the dimethylaminoalkyl group and the metallocenyl fragment and in case of the dimethylaminomethylferrocene also between the substituted and unsubstituted cyclopentadienyl rings. The data on the distribution of the isotopic label were used to ascertain the mechanism of fragmentation of the dimethylaminomethylferrocene under electron impact.

ChemInform Abstract: NEW DERIVATIVES OF CYMANTRENE AND FERROCENE

Chemischer InformationsdienstVolume 10, Issue 14 Organoelement Compounds ChemInform Abstract: NEW DERIVATIVES OF CYMANTRENE AND FERROCENE L. P. ASATIANI, L. P. ASATIANISearch for more papers by this authorD. S. ZURABISHVILI, D. S. ZURABISHVILISearch for more papers by this authorI. M. GVERDTSITELI, I. M. GVERDTSITELISearch for more papers by this author L. P. ASATIANI, L. P. ASATIANISearch for more papers by this authorD. S. ZURABISHVILI, D. S. ZURABISHVILISearch for more papers by this authorI. M. GVERDTSITELI, I. M. GVERDTSITELISearch for more papers by this author First published: April 3, 1979 https://doi.org/10.1002/chin.197914316Read the full textAboutPDF 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. Volume10, Issue14April 3, 1979 RelatedInformation

Pyrylium, pyridine, and N-phenylpyridinium derivatives of cyclopentadienyltricarbonylmanganese

2,4,6-Trisubstituted pyrylium salts containing a cymantrenyl substituent in the 6 position were synthesized by condensation of acetylcymantrene with chalcones. As compared with the corresponding pyrylium derivatives of ferrocene, the pyrylium salts obtained exchange a heteroatom more readily and are more stable. The pyrylium derivatives of cymantrene were converted to the corresponding pyridines by the action of ammonium acetate in glacial acetic acid or an aqueous solution of ammonia and to the corresponding N-phenylpyridinium salts by the action of aniline in acetic acid or alcohol.

Vinylidene complexes of transition metals : II. A new method of synthesis of vinylidene complexes. Cymantrene derivatives containing phenylvinylidene ligands

A rearrangement of transition metal acetylenic π-complexes into compounds with vinylidene n-ligands has been established. Compounds CpMn(CCHPh)-(CO) 2 and Cp 2Mn 2(μ-CCHPh)(CO) 4 with terminal and bridging phenylvinylidene (benzylidenecarbene) ligands respectively were obtained from the π-complexes CpMn(CO) 2(PhCCR) where R  H, Ph 3Ge or Ph 3Sn. Reactions leading to conversion of the terminal CCHPh group into a bridging ligand and vice versa were studied. Under the action of L  Ph 3P, (EtO) 3P or (PhO) 3P, substitution of CO groups in vinylidene complexes takes place and compounds CpMn(CCHPh)-(CO)L are formed. IR, 1H and 13C NMR spectra of the novel complexes are discussed. The data obtained indicate an electron-withdrawing property of the CCHPh ligand and stronger bonding of this ligand to the metal as compared with a CO group.

Polymorphism of mercury derivatives of cymantrene

The55Mn,35C1, and81Br NQR spectra of a number of mercury derivatives of cymantrene were studied. The insertion of the HgHal grouping into the cyclopentadienyl ring has little effect on the quadrupole constants of the central metal atom. 2. Two crystalline modifications each were detected for RHgCl and R2Hg, while phase transition was detected in R2Hg when the temperature was varied from 77 to 293°K. 3. RHgBr is also easily symmetrized in the absence of symmetrizing agents.

Contribution a l'etude des metaux asymetriques : V. Substitution photochimique des carbonyles du greffon Mn(CO) 3 dans des complexes cymantreniques; incidence sur la force des liaisons metal—ligand, diastereotopie et diastereoisomerie inherentes a la chiralite du manganese. Etude RMN

Various studies by p K a measurements, v (CO) frequencies and NMR data on the photochemical replacement of CO by various phosphines or phosphites provide information on the metal—ligand bond strength in the derivatives of cymantrene. For pseudo-tetrahedral complexes with an asymmetric manganese atom, the chirality at the metal atom and the consequent diastereotopy are shown by NMR. Several general NMR data bearing relation to 31P are also discussed.

Contribution a l'etude des metaux asymetriques III. Creation, en serie du cymantrene, d'une activite optique inherente a la chiralite du manganese

The photochemical substitution, by various phosphines or phosphites, of the carbonyl ligands of derivatives of cymantrene has been studied, giving evidence of the effect of the electron density on the metal for mono- or di-substitution. Optically active derivatives which are chiral at manganese have been synthesized and their enantiomeric stability ascertained.

The non-equivalence of chemical shifts of the diastereotopic carbons in the cyclopentadienyl ring of chiral monosubstituted cymantrene derivatives

The non-equivalence of chemical shifts of the diastereotopic carbons in the cyclopentadienyl ring of chiral monosubstituted cymantrene derivatives

Anwendung der Hochdruck-Fl�ssig-Fl�ssig-Chromatographic (LLC) in der Metallocenchemie

The High Pressure Liquid-Liquid-Chromatography (LLC) is an excellent technique for the qualitative and quantitative separation of isomeric and homologous metallocenes, as is shown with 55 various derivatives of benchrotrene, ferrocene and cymantrene.

Steric relations and the PMR spectra of monosubstituted derivatives of cymantrene having a chiral centre in the substituent

Steric relations and the PMR spectra of monosubstituted derivatives of cymantrene having a chiral centre in the substituent

Steric relations and the PMR spectra of monosubstituted derivatives of cymantrene having a chiral centre in the substituent

Steric relations and the PMR spectra of monosubstituted derivatives of cymantrene having a chiral centre in the substituent

Organometallic studies. Part XXV. Mass spectra of some mono-substituted cymantrenes

The spectra of eighteen cymantrene derivatives are reported and discussed. Fragmentation patterns are suggested and substantiated by the use of metastable peaks wherever such have been observed. The presence of the metal atom in many of the fragment ions observed appears to play an important role in determining stability and subsequent fragmentation paths of these ions. This is illustrated by the observation of several intramolecular rearrangements, involving the metal atom.