Cyclopentadienyleisen-komplexe mit P(OR)3-liganden; Synthese und spektroskopische charakterisierung

Reactions of reactive cyclopentadienyliron complexes C₅H₅Fe(CO)₂I, [C₅H₅Fe(CO)₂THF]BF₄, [C₅H₅Fe(CO)((CH₃)₂S)₂]BF₄ and [C₅H₅Fe(p-(CH₃)₂C₆H₄)]PF₆ with P(OR)₃ as ligands (R = CH₃, C₂H₅, i-C₃H₇ and C₆H₅) lead to the formation of the complex compounds C₅H₅Fe(CO)_2?n(P(OR)₃)_nI and [C₅H₅Fe(CO)_3?n(P(OR)₃)_n]X (n = 1, 2 and n = 1–3, X = BF₄, PF₆). Spectroscopic investigations (IR, ¹H, ¹³C and ³¹P NMR) indicate an increase of electron density on the central metal with increasing substitution of CO groups by P(OR)₃ ligands. The stability of the compounds increase in the same way.     

Funktionell substituierte zinnorganische verbindungen v. st]Phosphono- Und phosphonylmethyl-triorganostannane

The synthesis of phosphono- and phosphonylmethyl-triorganostannanes R₃SnCH₂P(O)(OR′)R′′ (R′′  OR′, C₆H₅) via an Arbuzov reaction of R₃SnCH₂I with P(OR′)₃ or C₆H₅P(OR′)₂ (R′′  CH₃, C₂H₅) is described. The new compounds have been studied with regard to their behaviour towards electrophilic (Br₂, HCl, HgBr₂) and nucleophilic (NaOH, LiAlH₄, LiR) agents. Their reaction with chlorophenylphosphines followed by reduction with LiAlH₄ yields the unsymmetrical methylenebis(phosphines) C₆H₅P(R)CH₂PH₂ (R  H, C₆H₅). The title compounds add to the carbonyl group of aldehydes and the CN bond of phenylisocyanate.     

Ligating properties of thionitrosoamines: IV. Cationic complexes of rhodium(I), rhodium(III), and ruthenium(II) containing N-thionitrosodimethylamine

The solvento species obtained by treatment of the complexes [Rh(1,5-cyclooctadiene)Cl]₂, [Rh(norbornadiene)Cl]₂, [Rh(CO)₂Cl]₂, C₅H₅Rh(CO)I₂, [C₅Me₅RhCl₂]₂, and [Ru(C₆H₆)Cl₂]₂ with AgPF₆ in acetone or acetonitrile react with a large excess of Me₂NNS to give the compounds [Rh(1,5-C₈H₁₂)-(SNNMe₂)₂]PF₆ (1a), [Rh(C₇H₈)(SNNMe₂)₂]PF₆ (1b), [Rh(CO)₂(SNNMe₂)₂]PF₆ (2), [C₅H₅Rh(SNNMe₂)₃](PF₆)₂ (3), [C₅Me₅Rh(SNNMe₂)₃](PF₆)₂ (4), and [Ru(C₆H₆(SNNMe₂)₃](PF₆) (5). If the thionitroso ligand is not preent in large excess decomposition often occurs. The use of AgClO₄ allows isolation of the perchlorate salts of 1a, 1b, 2, 4, and 5, and the complexes [C₅H₅Rh-(SNNMe₂)₂(ClO₄)ClO₄ (6) and Rh(1,5-C₈H₁₂)(SNNMe₂)(ClO₄) (7). In the H¹ NMR spectra the methyl protons of Me₂NNS are observed as two quadruplets, in the range δ 3.75–4.25 (⁴J(HH) ca. 0.7 Hz) because of restricted rotation around the NN bond. The rhodium(I) complexes (1a, 1b, and 2) reacts with PPh₃ or p-tolylPPh₂ to give labile products, and only [Rh(1,5-C₈H₁₂)(SNNMe₂)(PPh₃)]ClO₄ (8) and [Rh(1,5-C₈H₁₂)(SNNMe₂)(p-tolylPPh₂)]ClO₄ (9) were isolated and characterized.     

Carbonyl rhodium(I) complexes with α-diimines ligands

The reactions of [Rh(CO)₂Cl]₂ with α-diimines, RN=CR′-CR′=NR (R = c-Hex, C₆H₅, p-C₆H₄OH, p-C₆H₄CH₃, p-C₆H₄OCH₃, R′ = H; R = c-Hex, C₆H₅, p-C₆H₄OH, p-C₆H₄OCH₃; R′ = Me) in 2:1 Rh/R-dim ratio gave rise to ionic compounds [(CO)₂Rh.R-dim(R′,R′)][Rh(CO)₂Cl₂] which have been characterized by elemental analyses, electrical conductivity, ¹H-NMR and electronic and IR spectroscopy. Some of these complexes must involve some kind of metal-metal interaction. The complex [Rh(CO)₂Cl.c-Hex-dim(H,H)] has been obtained by reaction of [Rh(CO)₂Cl]₂ with the c-Hex-dim(H,H) ligand in 1:1 Rh/R-dim ratio. The reactions between [(CO)₂Rh.R-dim(H,H)][Rh(CO)₂Cl₂](R = c-Hex or p-C₆H₄OCH₃) with the dppe ligand have been studied. The known complex RhCl(CO)(PPh₃)₂ has been isolated from the reaction of [(CO)₂Rh.R-dim(H,H)]-[Rh(CO)₂Cl₂] (R = c-Hex or p-C₆H₄OCH₃) with PPh₃ ligand.     

Massenspektrometrische Untersuchungen an Organophosphorverbindungen. II—Elektronenstoßinduzierte Fragmentierungen von Tetraorganodiphosphandisulfiden

The behaviour under electron impact (70 eV) which includes some rearrangement processes of some tetraorganodiphosphanedisulfides R₂P(S)-P(S)R₂ (R ? CH₃, C₂H₅, n-C₃H₇, n-C₄H₉, C₃H₅, C₆H₅) and CH₃RP(S)–P(S)CH₃R (R ? C₂H₅, n-C₃H₇, n-C₄H₉, C₆H₅, C₆H₅, C₆H₅,CH₂) is reported and discussed. Fragmentation patterns which are consistent with direct analysis of daughter ions and defocusing metastable spectra are given. The atomic composition of many of the fragment ions was determined by precise mass measurements. In contrast to compounds R₃P(S) loss of sulphur is not a common process here. The first step in the fragmentation of these compounds is cleavage of one P–C bond and loss of a substituent R?. The second step is elimination of RPS leading to [R₂PS]⁺ from which the base peaks in nearly all the spectra arise. The phenyl substituted compounds give spectra with very abundant [(C₆H₅)₃P]^+. and [(C₆H₅)₂CH₃P]^+. ions respectively, resulting from [M]^+. by migration of C₆H₅. Rearrangement of [M]^+. to a 4-membered P-S ring system prior to fragmentation is suggested.     

Reactions of iridium and platinum complexes with N-sulfinyl compounds

The reactions of substituted N-sulfinylanilines with the complexes {Pt[P(C₆H₅₃]₂O₂} and {IrClCO[P(C₆H₅)₃]₂} have been reinvestigated. The former complex yields {Pt[P(C₆H₅)₃]₂SO₄} as the only isolable product in reactions with N-sulfinylaniline. In contrast to a previous report, Vaska's complex has been found not to react with C₆H₅NSO under anhydrous conditions. {Pt[P(C₆H₅)₃]₂-(C₂H₄)} reacts with N-sulfinyl compounds to give complexes of formula {Pt[P(C₆H₅)₃]₂-(RNSO)} where R = C₆H₅, p-O₂NC₆H₄, p-CH₃C₆H₄, or p-CH₃C₆H₄SO₂. {Pt[P(C₆H₅)₃]₃} reacts with C₆H₅NSO to give the same product obtained from reaction with the ethylene complex. Vaska's complex and its bromo analog form 1:1 adducts with p-O₂NC₆H₄NSO.     

Mononuclear Complexes of Platinum Group Metals Containing η6‐ and η5‐Cyclic Π‐Perimeter Hydrocarbon and Pyridylpyrazolyl Derivatives: Syntheses and Structural Studies

Piano‐stool‐shaped platinum group metal compounds, stable in the solid state and in solution, which are based on 2‐(5‐phenyl‐1H‐pyrazol‐3‐yl)pyridine ( L ) with the formulas [(η⁶‐arene)Ru( L )Cl]PF₆ {arene = C₆H₆ ( 1 ), p‐cymene ( 2 ), and C₆Me₆, ( 3 )}, [(η⁶‐C₅Me₅)M( L )Cl]PF₆ {M = Rh ( 4 ), Ir ( 5 )}, and [(η⁵‐C₅H₅)Ru(PPh₃)( L )]PF₆ ( 6 ), [(η⁵‐C₅H₅)Os(PPh₃)( L )]PF₆ ( 7 ), [(η⁵‐C₅Me₅)Ru(PPh₃)( L )]PF₆ ( 8 ), and [(η⁵‐C₉H₇)Ru(PPh₃)( L )]PF₆ ( 9 ) were prepared by a general method and characterized by NMR and IR spectroscopy and mass spectrometry. The molecular structures of compounds 4 and 5 were established by single‐crystal X‐ray diffraction. In each compound the metal is connected to N1 and N11 in a k² manner.     

Synthesis of new phosphorus ylides: Spectroscopic and X‐ray structural studies

Stable phosphoranes, Ar₃P = CHCOR (R = C₆H₅, C₆H₄NO₂, C₆H₄OCH₃, CH₃, OCH₂C₆H₅; Ar = p‐tolyl or phenyl), have been C‐acylated by acetic anhydride to obtain new types of phosphorus ylides. Synthesis and characterization of six phosphorus ylides of the type Ar₃PC(COCH₃)(COR) are reported. The reaction of {(p‐tolyl)₃PCHCOC₆H₅} ( I ), {(p‐ tolyl)₃PCHCOC₆H₄NO₂} ( II ), {Ph₃PCHCOC₆H₄NO₂} ( III ), {Ph₃PCHCOC₆H₄OCH₃} ( IV ), {(p‐tolyl)₃PCHCOCH₃} ( V ), and {Ph₃PCHCOOCH₂C₆H₅} ( VI ) with acetic anhydride in dry chloroform as solvent gives (p‐tolyl)₃PC(COMe)(COC₆H₅), α‐acetyl‐α‐benzoylmethy‐lenetriphenylphosphorane ( 1 ), {(p‐tolyl)₃PC(COMe) (COC₆H₄NO₂)} ( 2 ), {Ph₃PC(COMe)(COC₆H₄NO₂)} ( 3 ), {Ph₃PC(COMe)(COC₆H₄OCH₃)} ( 4 ), {(p‐tolyl)₃ PC(COCH₃)₂} ( 5 ), and {Ph₃PC(COMe)(COOCH₂ C₆H₅)} ( 6 ). Single crystal X‐ray analyses for ylides 2 , 5 , and 6 reveal the monoclinic ( 2, 5 ) and triclinic ( 6 ) crystal systems. Characterization of the obtained compounds was also performed by elemental analysis, IR, ¹H, ³¹P, and ¹³C NMR. The geometries of these compounds have been investigated using density functional theory (DFT). In addition, electronic parameters of these compounds such as HOMO and LUMO energy, Mulliken partial charge, and dipole moment were obtained. In this paper, the reactivity of these ylides is discussed in regard to the aforementioned data. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:475–485, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20633     

Monodentate phosphites with carbohydrate substituents and their application in rhodium catalysed asymmetric hydrosilylation reactions

Several monodentate phosphites derived from d-glucofuranose were prepared and examined as ligands in the rhodium catalysed enantioselective hydrosilylation of acetophenone. A substantial variation in the e.e. values, from racemic to 58% e.e., was seen depending on the nature of the phosphite ligand used and the ligand to metal ratio. The reactivity of the selected phosphite P(DAG)₃ towards [Rh(μ-Cl)(COD)]₂ and [Rh(μ-Cl)(C₂H₄)₂]₂ (DAG=(1:2;5:6)-di(O-isopropylidene)-d-glucofuranosyl) allowed the synthesis of monosubstitued Rh(Cl)(COD)P(dag)₃ and [Rh(μ-Cl)(C₂H₄)P(dag)₃]₂ complexes, and the disubstituted Rh(Cl)(P(dag)₃)₂ and Rh(Cl)(C₂H₄)(P(dag)₃)₂ complexes. This study indicated that the disubstituted compounds offer better enantioselectivities than the monosubstituted ones.     

Polymerization of propadiene. III. Catalyst systems based on various rhodium (I) complexes

The polymerization of propadiene to 1,2-polyallene by various Rh(I) based catalysts is described and discussed. Also the interrelations between these Rh(I) complexes are discussed and an overall reaction scheme is given. A mechanism is put forward in which the formation of a common intermediate from propadiene and different Rh(I) complexes is the rate determining step. It is found that the activity decreases in the order: cis-Rh(CO)₂P(C₆H₅)₃Cl > [Rh(CO)₂Cl]₂ > Rh(CO)₃Cl. The complexes Rh[P(C₆H₅)₃]₂(CO)Cl and Rh[P(C₆H₅)₃]₃Cl proved to be inactive in the polymerization of propadiene.     

Fast atom bombardment mass spectrometry of non-volatile organometallic compounds. Rhodium,iridium and platinum complexes containing a cumulene ligand

Fast atom bombardment (FAB) mass spectrometry has been used to examine a series of rhodium, iridium and platinum organimetallic complexes, in which a cumulene ligand is attached to the metal in either σ-or π-bonding fashion. The most intense ion formed in the rhodium and platinum series is the metal-bis(triphenylphosphine) ion, while the [Ir(P(C₆H₅)₃)₂CO]⁺ ion is most intense for the iridium series. The platinum complexes show the most intense molecular ion peaks (up to 35% relative intensity), while the rhodium complexes show the least intense molecular ion peaks. The primary fragmentations of all these complexes occur at the metal-ligand bonds. The cumulenic ligand is lost as an impact unit in all cases. The FAB mass spectra of Rh(P(C₆H₅)₃)₃Cl (Wilkinson's catalyst), Ir(P(C₆H₅)₃)₂COCl (Vaska's compound), Rh(P(C₆H₅)₃)₂COCl and Pt(P(C₆H₅)₃)₂(C₂H₄)–synthetic precursors or related compounds to the organometallic complexes examined here–are included for comparison.     

Synthese und NMR.-Spektren von neuartigen Lanthanoid-Kobalt-Sandwichkomplexen

Synthesis and NMR. Spectra of Novel Lanthanide-Cobalt Sandwich Compounds The reaction of [(C₅H₅)Co{P(O)(OR)₂}₂{P(OH)(OR)₂}] ( 3 , R = CH₃, C₂H₅) with lanthanide(III) compounds yields the cationic trinuclear complexes [{(C₅H₅)Co[P(O)(OR)₂]₃}₂Ln]^⊕X^? ( 2 , R = CH₃, C₂H₅; Ln = La, Eu, Pr; X = BF₄, BPh₄). According to thermogravimetric and NMR. studies these compounds do not contain additional coordinated water molecules. It is therefore supposed that the central lanthanide ion has a regular sixfold coordination of phosphoryl ligands. The ³¹P- and ¹H-NMR. spectra of 2 (R = CH₃; Ln = La, Eu, Pr) and 3 are discussed. It can be shown that the Fermi contact shift as well as the coordination shift make significant contributions to the observed lanthanide induced shift of the cyclopentadienyl signal.The dominating influence of the Fermi contact interaction on the ³¹P chemical shift is in accord with theoretical considerations and comparable experimental values. The temperature dependence of the proton chemical shifts of 2 (R = CH₃; Ln = Eu) is also discussed.     

Oxidative addition of different electrophiles with rhodium(I) carbonyl complexes of unsymmetrical phosphine–phosphine monoselenide ligands

Dimeric chlorobridge complex [Rh(CO)₂Cl]₂ reacts with two equivalents of a series of unsymmetrical phosphine–phosphine monoselenide ligands, Ph₂P(CH₂)_nP(Se)Ph₂ {n = 1( a ), 2( b ), 3( c ), 4( d )}to form chelate complex [Rh(CO)Cl(P∩Se)] ( 1a ) {P∩Se = η²‐(P,Se) coordinated} and non‐chelate complexes [Rh(CO)₂Cl(P～Se)] ( 1b–d ) {P～Se = η¹‐(P) coordinated}. The complexes 1 undergo oxidative addition reactions with different electrophiles such as CH₃I, C₂H₅I, C₆H₅CH₂Cl and I₂ to produce Rh(III) complexes of the type [Rh(COR)ClX(P∩Se)] {where R = ? C₂H₅ ( 2a ), X = I; R = ? CH₂C₆H₅ ( 3a ), X = Cl}, [Rh(CO)ClI₂(P∩Se)] ( 4a ), [Rh(CO)(COCH₃)ClI(P～Se)] ( 5b–d ), [Rh(CO)(COH₅)ClI‐(P～Se)] ( 6b–d ), [Rh(CO)(COCH₂C₆H₅)Cl₂(P～Se)] ( 7b–d ) and [Rh(CO)ClI₂(P～Se)] ( 8b–d ). The kinetic study of the oxidative addition (OA) reactions of the complexes 1 with CH₃I and C₂H₅I reveals a single stage kinetics. The rate of OA of the complexes varies with the length of the ligand backbone and follows the order 1a > 1b > 1c > 1d . The CH₃I reacts with the different complexes at a rate 10–100 times faster than the C₂H₅I. The catalytic activity of complexes 1b–d for carbonylation of methanol is evaluated and a higher turnover number (TON) is obtained compared with that of the well‐known commercial species [Rh(CO)₂I₂]^?. Copyright © 2006 John Wiley & Sons, Ltd.     

Bis(dimethyl sulfoxide‐S)tetrakis(μ‐p‐hydroxybenzoato‐O:O′)dirhodium(II)–tetrakis(μ‐butyrato‐O:O′)bis(dimethyl sulfoxide‐S)dirhodium(II) cocrystal ethanol disolvate

The title structure, [Rh₂(C₇H₅O₃)₄(C₂H₆OS)₂]·[Rh₂(C₄H₇­O₂)₄(C₂H₆OS)₂]·2C₂H₆O, contains two discrete neutral Rh–Rh dimers cocrystallized as the ethanol disolvate. Each dimer is situated on an inversion center. The butyrate chain displays disorder in one C‐atom position. In each dimer, the di­methyl sulfoxide ligand (dmso) is bound via S, as expected. The ethanol is a hydrogen‐bond acceptor for one p‐hydroxy­benzoate hydroxyl group and acts as a hydrogen‐bond donor to the dmso O atom of a neighboring p‐hydroxy­benzoate dirhodium complex. A third hydrogen bond is formed from the other p‐hydroxy­benzoate hydroxyl group to the dmso O atom of a butyrate–dirhodium complex.     

Regiospecific Formation and Unusual Optical Properties of 2,5‐Bis(arylethynyl)rhodacyclopentadienes: A New Class of Luminescent Organometallics

A series of 2,5‐bis(arylethynyl)rhodacyclopentadienes has been prepared by a rare example of regiospecific reductive coupling of 1,4‐(p‐R‐phenyl)‐1,3‐butadiynes (R?H, Me, OMe, SMe, NMe₂, CF₃, CO₂Me, CN, NO₂, ?C?C‐(p‐C₆H₄?NHex₂), ?C?C?(p‐C₆H₄?CO₂Oct)) at [RhX(PMe₃)₄] ( 1 ) (X=?C?C?SiMe₃ ( a ), ?C?C‐(p‐C₆H₄?NMe₂) ( b ), ?C?C?C?C?(p‐C₆H₄?NPh₂) ( c ) or ?C?C?{p‐C₆H₄‐C?C?(p‐C₆H₄‐N(C₆H₁₃)₂)} ( d ) or Me ( e )), giving the 2,5‐bis(arylethynyl) isomer exclusively. The rhodacyclopentadienes bearing a methyl ligand in the equatorial plane (compound 1 e ) have been converted into their chloro analogues by reaction with HCl etherate. The rhodacycles thus obtained are stable to air and moisture in the solid state and the acceptor‐substituted compounds are even stable to air and moisture in solution. The photophysical properties of the rhodacyclopentadienes are highly unusual in that they exhibit, exclusively, fluorescence between 500–800 nm from the S₁ state, with quantum yields of Φ=0.01–0.18 and short lifetimes (τ=0.45–8.20 ns). The triplet state formation (Φ_ISC=0.57 for 2 a ) is exceptionally slow, occurring on the nanosecond timescale. This is unexpected, because the Rh atom should normally facilitate intersystem crossing within femto‐ to picoseconds, leading to phosphorescence from the T₁ state. This work therefore highlights that in some transition‐metal complexes, the heavy atom can play a more subtle role in controlling the photophysical behavior than is commonly appreciated.     

Direktsynthese von orthometallierten Ketonen des Typs RCO (o-C6H4)Mn(CO)4−nLn (R = Alkyl- und Arylrest,n = 0, 1, 2, L = Ligand)

Direct Synthesis of Orthometallated Ketones of the Type RCO(o-C₆H₄)Mn(CO)_4?nL_n (R = Alkyl and Aryl Groups, n = 0, 1, 2, L = Ligand) The starting materials of the type RMn(CO)_5?nL_n und (C₆H₅)₂ Hg react to the products of the type RCO(o-C₆H₄)Mn(CO)_4?nL_n[n = 0, R = Ch₃, C₂H₅, C₃H₇, C₆H₅,CH₂; R = C₆H₅, n = 1, L = E(C₆H₅)₃, E = P, As, Sb; R = C₆H₅, n = 2, L = P(OR′)₃, R′ = C₆H₅, CH₃, C₂H₅, C₃H₇]. Steps of their complex reaction pathway are proposed. These orthometallated substances have been characterized by means of ¹H-n.m.r., i.r. and u.v. spectroscopic measurements. The determination of the molecular structure of the two compounds RCO(o-C₆H₄)Mn(CO)₃L [R = C₂H₅, L = CO; R = C₆H₅, L = As(C₆H₅)₃] show that both contain a planar heterocyclic five-membered ring of the type .     

Metallorganische Verbindungen mit N-substituierten 3-Hydroxy-2-methyl-4-pyridon-Liganden: quadratisch-planare Rhodium(I)-, Iridium(I)- und Palladium(II)-Komplexe

Organometallic Compounds with N -substituted 3-Hydroxy-2-methyl-4-pyridone Ligands: square planar Rhodium(I), Iridium(I), and Palladium(II) Complexes Reactions of [(OC)₂MCl]₂ (M = Rh, Ir) or [(cod)RhCl]₂ with the anions of N-Aryl or N-Alkyl substituted 3-hydroxy-2-methyl-4-pyridones (O–O′) yield complexes of the general formula [L₂M(O–O′)]. Compounds of this type are also available from reactions of [(OC)₂Rh(acac)] with the corresponding neutral ligands. Substitution of one carbonyl-ligand of the N-phenyl complex [(OC)₂Rh(C₁₂H₁₀NO₂)] ( 2 ) with cyclooctene affords [(OC)(C₈H₁₄)Rh(C₁₂H₁₀NO₂)] ( 8 ). The palladium complexes [(R₃P)Pd(O–O′)Cl] (R = Et, Bu), [(C₆H₄CH₂NMe₂) · Pd(O–O′)] and [(Et₃P)₂Pd(O–O′)]BF₄ ( 9 – 12 ) were synthesized from [(R₃P)PdCl₂]₂, [(C₆H₄CH₂NMe₂)PdCl]₂ or [(Et₃P)PdCl₂]. The structures of the N-methyl compounds [(OC)₂Rh(C₇H₈NO₂)] ( 1 ) and [(Ph₃P)Pd(C₇H₈NO₂)Cl] ( 9 ) were determined by single crystal X-ray diffraction.     

Reduction of α,β unsaturated carbonyl compounds by Ni–BH4

The reduction of α,β unsaturated carbonyl compounds by sodiumborohydride is catalysed by Ni(bpy)Cl₂ (bpy=2,2′-bipyridine). Various carbonyl compounds having the general formula R₁CH=CHCRO [where R₁, R=C₆H₅, H; p-MeO---C₆H₄---,C₆H₄; p-CH₃---C₆H₄, C₆H₅; (m-OMe---)(p-OMe---)C₆H₃, C₆H₅; C₆H₅, (CH₃)₂CH---; CH₃, H; m-Br---C₆H₄---, C₆H₅] are reduced to corresponding allylicalcohol [R₁CH=CHCRHOH] at 25°C within half an hour. During these reductions the double bond is partially reduced to give saturated alcohols as minor products having the molecular formula R₁CH₂CH₂CRHOH. The reduction of trans-3-phenyl-2-propenal with NaBH₄ and catalytic amounts of Ni(bpy)Cl₂ in solvents containing active deuterium (D₂O, CD₃OD), leads to the partial incorporation of deuterium at the α and γ positions to give C---D bonded alcohols.     

Ligandenverdrängungsreaktionen von Kobalt-dicyclopentadienyl mit tertiären Phosphiten – Darstellung und Eigenschaften der Komplexe C5H5Co[P(OR)3]2

The reaction of Co(C₅H₅)₂ with tertiary phosphites mainly gives the half-sandwich type compounds C₅H₅Co[P(OR)₃]₂ (R = CH₃, C₂H₅, C₆H₅), which are characterised by means of their IR., UV., and NMR. spectroscopic data. The mass spectra of the new compounds are discussed.     

2, 4‐Dimethylpenta‐1, 3‐dien‐ und 2, 4‐Dimethylpentadienyl‐Komplexe des Rhodiums und Iridiums

2, 4‐Dimethylpenta‐1, 3‐diene and 2, 4‐Dimethylpentadienyl Complexes of Rhodium and Iridium The complexes [(η⁴‐C₇H₁₂)RhCl]₂ ( 1 ) (C₇H₁₂ = 2, 4‐dimethylpenta‐1, 3‐diene) and [(η⁴‐C₇H₁₂)₂IrCl] ( 2 ) were obtained by interaction of C₇H₁₂ with [(η²‐C₂H₄)₂RhCl]₂ and [(η²‐cyclooctene)₂IrCl]₂, respectively. The reaction of 1 or 2 with CpTl (Cp = η⁵‐C₅H₅) yields the compounds [CpM(η⁴‐C₇H₁₂)] ( 3a : M = Rh; 3b : M = Ir). The hydride abstraction at the pentadiene ligand of 3a , b with Ph₃CBF₄ proceeds differently depending on the solvent. In acetone or THF the “half‐open” metallocenium complexes [CpM(η⁵‐C₇H₁₁)]BF₄ ( 4a : M = Rh; 4b : M = Ir) are obtained exclusively. In dichloromethane mixtures are produced which additionally contain the species [(η⁵‐C₇H₁₁)M(η⁵‐C₅H₄CPh₃)]BF₄ ( 5a : M = Rh; 5b : M = Ir) formed by electrophilic substitution at the Cp ring, as well as the η³‐2, 4‐dimethylpentenyl compound [(η³‐C₇H₁₃)Rh{η⁵‐C₅H₃(CPh₃)₂}]BF₄ ( 6 ). By interaction of 2, 4‐dimethylpentadienyl potassium with 1 or 2 the complexes [(η⁴‐C₇H₁₂)M(η⁵‐C₇H₁₁)] ( 7a : M = Rh; 7b : M = Ir) are generated which show dynamic behaviour in solution; however, attempts to synthesize the “open” metallocenium cations [(η⁵‐C₇H₁₁)₂M]⁺ by hydride abstraction from 7a , b failed. The new compounds were characterized by elemental analysis and spectroscopically, 4b and 5a also by X‐ray structure analysis.