Reaction Of Cp Research Articles

Early-metal macrocycles as metalloligands: synthesis and structure of dimeric zirconocene dithiolates Cp2Zr(.mu.-S(CH2)nS)2ZrCp2 (n = 2, 3) and their silver complexes [(Cp2Zr(.mu.-S(CH2)nS)2ZrCp2)Ag]BPh4 (n = 2, 3)

The reactions of Cp 2 ZrMe 2 with the dithiols HS(CH 2 ) n SH (n=2-4) and o- and m-HSCH 2 C 6 H 4 CH 2 SH proceed with evolution of methane, affording the insoluble zirconocene dithiolate derivatives. In the case of HS(CH 2 ) n SH, where n=2 and 3, the products can also be synthesized via reaction of Cp 2 ZrMe 2 or [Cp 2 ZrHCl] n with HS(CH 2 ) n SSiMe 3 (n=2,3). Crystallographic studies of two of these products show that there are bimetallic compounds

Organolanthanid(II)-Chemie: Synthese und Struktur von [Cp2*Sm(μ-OC)2FeCp*

Organolanthanide(II) Chemistry: Synthesis and Structure of [Cp*Sm(μ-OC)2FeCp*]2 The tetranuclear complex [Cp*Sm(μ-OC)2FeCp*]2 (3) has been prepared by reaction of Cp*2Sm(THF)2 with [Cp*Fe(CO)2]2 and structurally characterized by single-crystal X-ray diffraction.

Reactivity of ruthenium trihydrides with Broensted and Lewis acids. X-ray crystal structures of {Cp*Ru[C6H9P(C6H11)2]}BF4 and {{Cp*RuH[P(C6H11)3]}(.mu.-H)2Cu(.mu.-Cl)}2. Evidence for exchange coupling between two hydrogen atoms

The reaction of Cp*RuH 3 (PPh 3 ) (1a; Cp*=C 5 Me 5 ) with P(OMe) 3 produces Cp*RuH(PPh 3 )[P(OMe) 3 ] (2), whereas no reaction occurs between 1a and pyridine. The protonation of 1a by HBF 4 /Et 2 O yields [Cp*RuH 2 (PPh 3 ) 2 ]BF 4 (3), but the same reaction with Cp*RuH 3 [P(c-C 6 H 11 ) 3 ] (1b) leads to the evolution of 3 mol of H 2 and formation of {Cp*Ru[C 6 H 9 P(c-C 6 H 11 ) 2 ]}BF 4 (4). Complex 4 contains a cyclohexenyl group coordinated through the C=C double bond and a strong agostic interaction, as demonstrated by both and X-ray crystal structure determination and 1 H and 13 C NMR studies. The protonation of 1b with CF 3 COOH produces Cp*Ru(OCOCF 3 [P(c-C 6 H 11 ) 3 ] (5), in which the trifluoroacetato group is bidentate. The reactions of 1b with the Lewis acids [CuCl] n and [Cu(MeCN) 4 ]BF 6 lead to {[Cp*Ru[P(c-C 6 H 11 ) 3 ]H-(μ-H) 2 ]Cu(μ-Cl)} 2 (6), which was characterized by X-ray crystallography, and to {[Cp*Ru[P(c-C 6 H 11 ) 3 ]H-(μ-H) 2 ] 2 Cu}PF 6 (7), respectively

Oxidative alkylation of (η 5-C 5Me 5) 2TiR (R = Cl, Me, Et, CHCH 2, Ph, OMe, NC(H) tBu) to (η 5-C 5Me 5) 2Ti(Me)R by group 12 organometallic compounds MMe 2

Oxidative alkylation of Cp * 2TiX (Cp *: η 5-C 5Me 5; X = OMe, Cl, NC(H) tBu) and Cp * 2TiMe by CdMe 2 or ZnMe 2 gives diamagnetic Cp * 2Ti(Me)X and Cp * 2TiMe 2 respectively, and cadmium or zinc. The reactions of Cp * 2TiR (R = Et, CHCH 2, Ph) with MMe 2 (M = Cd, Zn) give statistical mixtures of Cp * 2Ti(Me)R, Cp * 2TiMe 2 and Cp * 2TiR 2. Dimethylmercury does not react with Cp * 2TiX.

Distinct chemical reactivities of tungsten propargyl and allenyl complexes: novel carbon-carbon bond formation of the allenyl ligand and molecular structure of a tungsten complex containing an azametallacyclobutane ring

The reactions of Cp(CO) 3 WCH=C=CH 2 with excess methylamine and with 1 equiv of ethanol produce the aza metallacycle complex Cp(CO) 2 WCH-(CONHMe) CHMeNHMe and Cp(CO) 2 W(η 3 -CH-(COOC 2 H 5 ) CHCH 2 ) respectively

Coupling of alkynes on a cluster core: reaction of Cp'2Mo2Co2(CO)4S3 with alkynes

Cp' 2 Mo 2 Co 2 (CO) 4 S 3 (1; Cp'=C 5 H 4 CH 3 ) reacts with phenylacetylene to yield the cluster Cp' 2 Mo 2 Co 2 -(CO) 2 S 3 (PhCCH) (2), which contains a μ 3 -η 2 -bound alkyne. Cluster 2 adds another 1 mol of alkyne to yield the cluster Cp' 2 Mo 2 Co 2 (CO) 2 S 3 (PhCCH) 2 (3), in which the alkynes are coupled to form a molybdacyclopentadiene with each double bond coordinated to a cobalt atom

Isolation of [CpCr(CO)3]2(μ-SnCl2) and CpCrCl2(THF) from the insertion-displacement of Se in Cp2Cr2(CO)4Se with SnCl2. Crystal structure of CpCrCl2(CH3CN) (Cp = η5-C5H5)

Abstract The reaction of Cp 2 Cr 2 (CO) 4 Se with SnCl 2 in tetrahydrofuran results in the formation of Cp 2 Cr 2 (CO) 6 SnCl 2 and CpCrCl 2 (THF) as the main stable products. The latter recrystallises from CH 3 CN as CpCrCl 2 (CH 3 CN) in the monoclinic, space group P 2 1 / a , a 12.868(6), b 5.863(2), c 12.875(5) A, β 102.97(3)°, Z = 4, R = 0.033 (637 F ).

Synthesis of monomeric (.eta.5-pentamethylcylopentadienyl)platinum(IV) methyl and bromo complexes and of [hydrotris(3,5-dimethyl-7-pyrazolyl)borato]trimethylplatinum

The reaction of Cp*MgCl{center dot}THF (Cp* = C{sub 5}Me{sub 5}) with 1 equiv of PtMe{sub 3}I and PtMe{sub 2}Br{sub 2} produces Cp*PtMe{sub 3} (1) and Cp*PtMe{sub 2}Br (2), respectively. Reaction of 2 with Br{sub 2} produces Cp*PtMeBr{sub 2} (3) in good yield. The structures of 2 and 3 have been determined by x-ray crystallography, and the crystal structure data are reported. Complex 2 crystallizes in the monoclinic space group, P2{sub 1}/m, and complex 3 crystallizes in the monoclinic space group, P2{sub 1}/m. The molecules reside on mirror planes and are monomeric pseudotetrahedral Pt(IV) complexes with piano stool type geometries and {eta}{sup 5}-Cp* groups. Both molecules have Br atoms on the mirror. This leads to a disorder of the Me and the second Br positions in complex 3. The average Pt-C(Cp*) bond length is 2.25 (7) {angstrom} in 2 and 2.22 (4) {angstrom} in 3. The Pt-C(Me) and Pt-Br bond lengths in 2 are 2.07 (2) and 2.498 (2) {angstrom}, respectively. The ordered Pt-Br bond length in 3 is 2.496 (2) {angstrom}. Treatment of 1 with halogens results in the cleavage of the Pt-Cp* bond. The reaction of PtMe{sub 3}I with KTp* (Tp* = (HB(3,5-dimethylpyrazolyl){sub 3}){sup {minus}}) in thf gives Tp*PtMe{submore » 3} (4) in almost quantitative yield. The reaction of 4 with Br{sub 2} brominates the 4-position of the pyrazolyl ring only. 28 refs., 2 figs., 5 tabs.« less

Synthese und strukturelle charakterisierung von übergangsmetallsulfidclustern mit Cp ★Mo- (Cp ★ = C 5Me 5), CuCl- und Fe(NO)-baugruppen

The reaction of Cp ★ 2Mo 2S 4 ( 1) (Cp ★ = η 5-C 5Me 5) with CuCl gives the polynuclear clusters of Cp ★ 2Mo 2CuClS 4 ( 2, 4) and Cp ★ 2Mo 2Cu 2Cl 2S 4 ( 3, 5) under expansion of the MoS skeleton. The structures of these clusters are determined by the structures of the Mo-substrates ( 1A + CuCl → 2 + 3; 1C + CuCl → 3 + 5), thus permitting elucidation of the reaction pathway. The 62e-cluster 3 possesses a distorted cuban-like M 4S 4 core with 5 MM bonds as shown by an X-ray diffraction study. One or two CuCl moieties are replaced by Fe(NO) when 3 is irradiated in the presence of [N(PPh 3) 2][Fe(CO) 3NO]. In a metathetical reaction with NaSPh, 3 gives Cp ★ 2Mo 2Cu 2(SPh) 2S 4 ( 8).

Reactions of bis(cyclopentadienyl)dimethylzirconium with fluorocarbon acids. Structure, dynamic properties, and zirconium-91 NMR spectra of (C5H5)2Zr[HC(SO2CF3)2-O,O'][HC(SO2CF3)2-O

Reaction of Cp 2 Zr(CH 3 ) 2 with 1 and 2 equiv of fluorocarbon acids such as H 2 C(SO 2 CF 3 ) 2 yields Cp 2 Zr(CH 3 )[HC(SO 2 CF 3 ) 2 ] and Cp 2 Zr[HC(SO 2 CF 3 ) 2 ] 2 , respectively. The structure of the latter compound demonstrates two HC(SO 2 CF 3 ) 2 ligands. One is bidentate and the other one monodentate, both being bonded to Zr through the sulfone oxygen atoms. The two types of ligands interconvert rapidly on the NMR time scale. 91 Zr chemical shifts are reported

Reduction of tungsten complexes with primary phosphines and lithium dialkyl phosphides. X-ray crystal structures of [(Cp*WCl 2) 2·( t-Bu 2PP t-Bu 2) 2], [(Cp*WCl 4)(H 2PPh)], [{(PhN)WCl 2(PMe 3) 2} 2(μ-N 2)] and trans-WCl 4(H 2P t-Bu) 2 (Cp* = η 5-C 5Me 5)

The reduction of several high oxidation state tungsten halide complexes by lithium organophosphides and primary phosphines is described. Reaction of Cp*WCl 4 (Cp* = η5-C 5Me 5) with t-Bu 2PLi (4 equiv.) results in reduction of the metal and coupling of t-Bu 2P units to form a mixture of [Cp*WCl 2] 2 and t-Bu 2PP t-Bu 2 which co-crystallize as [(Cp*WCl 2) 2·( t-Bu 2PP t-Bu 2) 2] ( 1). There are no close intermolecular contacts between the tungsten(III) chloride-bridged dimer (Cp*WCl 2) 2 and ( t-Bu 2PP t-Bu 2) in the solid state. In the crystal structure of 1 the diphosphine exists in the gauche conformation found in other structurally characterized diphosphines. The (Cp*WCl 2) 2 dimer has all four chloride ligands in bridging positions. Reaction of [Cp*WCl 4] 2 with 2 equiv. of Ph(H)PLi forms the monomeric phosphine adduct (Cp*WCl 4) (H 2PPh)] ( 2) in 50% yield. The reaction of WCl 6 wi th excess t-BuPH 2 in dichloromethane gives trans-WCl 4(H 2P t-Bu) 2 ( 3). Reaction of [(PhN)Cl 3W(PMe 3) 2] with t-Bu 2PLi (2 equiv.) under nitrogen leads to reduction and formation of the μ-N 2 bridged W(IV) dimer [{(PhN)WCl 2(PMe 3) 2} 2(μ-N 2)] ( 4) in which the WNNW core is virtually linear. Crystal data for 1: C 52H 102P 4Cl 4W 2, M = 1360.8, monoclinic, P2 1/ n (No. 14), a = 8.309(9), b = 24.50(1), c = 15.117(8) Å, β = 95.98(1)°, U = 3060.5 Å 3, Z = 2, R = 0.0385, R w = 0.0474. Crystal data for 2: C 16H 21PCl 4W, M = 569.98, monoclinic, P2 1/ c (No. 14), a = 8.776(9), b = 16.310(6), c = 16.580(1) Å, β = 101.21(6)°, U = 2327.8 Å 3, Z = 4, R = 0.046, R w = 0.069. Crystal data for 3: C 8H 20 P 2Cl 4W, M = 503.85, monoclinic, C2 (No. 5), a = 11.1 36(5), b = 8.218(7), c = 9.832(8) Å, β = 93.20(6)°, U = 898.29 Å 3, Z = 1, R = 0.0330, R w = 0.0369. Crystal data for 4: C 24H 46P 4Cl 4N 4W 2, M = 1024.07, monoclinic, P2 1/ c (No. 14), a = 15.702(2), b = 12.580(2), c = 19.416(4) Å, β = 94.41(1)°, U = 3823.9 Å 3, Z = 4, R = 0.043, R w = 0.051.

Synthesis and chemistry of cationic alkyl, alkenyl, and allyl complexes derived from the soluble, cationic hydride (C5H4Me)2Zr(H)(THF)+

Reaction of Cp' 2 Zr(CH 2 Ph) 2 (Cp'=C 5 H 4 Me) with [Cp' 2 Fe][BPh 4 ] in THF produces the cationic benzyl complex [Cp' 2 Zr(CH 2 Ph)(THF)][BPh 4 ] (4) which contains a normal η 1 -benzyl ligand. Hydrogenolysis of 4 in THF solution (1 atm of H 2 , 23 o C) produces the soluble cationic hydride complex [Cp' 2 Zr(H)-(THG)][BPh 4 ] (5). Hydride 5 reacts with olefins H 2 C=CH 2 R to yield cationic alkyl complexes [Cp' 2 Zr-(CH 2 CH 2 R)(THF)][BPh 4 ] (8a, R=H; 8b, R=Me; 8c, R=Et), with 2-butyne to give the cationic 2-butenyl complex [Cp' 2 Zr{(E)-C(Me)=C(H)(Me)}(THF)][BPh 4 ] (9), and with allene to give the allyl complex [Cp' 2 Zr(η 3 -C 3 H 5 )(THF)][BPh 4 ] (13)

Reactions of vinylidene and allenylidene cymantrene derivatives with isonitriles

Isocyanides (RNC) insert into the MC bond in Cp(OC) 2MnCCHPh (I), to give the intermediates Cp(OC) 2Mn(RNCCHPh), R = t-Bu (II), C 6H 11 (III), CH 2Ph (IV). The reaction of II–IV with H 2O gives Cp(OC) 2Mn[π- cis- Ph(H)CC(H)C(O)NHR], R = t-Bu (V), C 6H 11 (VI), CH 2Ph (VII). Reaction of III with Et 2NH forms Cp(OC) 2Mn[π-Ph(H)CCC(NEt 2)NHC 6H 11], which upon reaction with H 2O yields VI. The possibility of eliminating π-olefin ligands from V or VII by reaction with n-donors (Py, PPh 3) is shown. Reaction of Cp(OC) 2MnCCCPh 2 (VIII) with t-BuNC gives Cp(OC) 2Mn[π-Ph 2CCCHC- (O)NH-t-Bu] (IX).

Formal transfers of hydride from carbon-hydrogen bonds. Synthesis, structure, and reactions of [Cp(CO)2FeCH2]3CH

The reaction of Cp(CO) 2 FeNa with (CH 3 SO 2 OCH 2 ) 3 CH provided [Cp(CO) 2 FeCH 2 ] 3 CH (3) in 50% yield. Thermal decomposition of compound 3 occurred rapidly in solution at 25 o C and produced approximately equimolar amounts of [Cp(CO) 2 Fe] 2 and dicarbonyl (cyclopentadienyl) (cyclopropylmethtyl) iron. These products presumably result from decarbonylation of compound 3, formation of carbonyl-bridged intermediate, and reductive elimination. The reaction of compound 3 with Ph 3 C + PF 6 − yielded the Cp(CO) 2 Fe + complex of Cp(CO) 2 FeCH 2 CH 2 CH=CH 2

Synthesis and cis-trans isomerism of (pentamethylcyclopentadienyl)rhenium(III) halide complexes formed by oxidative addition of X2 or HX (X = chlorine, bromine, iodine) to (.eta.5-C5Me5)Re(CO)2(PMe3) or (.eta.5-C5Me5)Re(CO)(PMe3)(N2)

The cis isomers of the dihalide complexes have been synthesized from the reaction of Cp * Re(CO)(PMe 3 )(N 2 ) with X 2 in hexane (Cp * =η 5 -C 5 Me 5 ). The trans isomer was synthesized by treatment of trans-Cp * Re(CO)(PMe 3 )(H)(Br) with N-bromosuccinimide

Preparation, crystal structure, absolute configuration, and conformational analysis of (−) 436-( S)-(−)-diphenyl-1-phenylethylaminophosphine(η 5-pentamethylcyclopentadienyl)-dimethylphosphonato)cobalt(III)

Reaction of Cp ★CoI 2(P(OMe) 3) 8 with the chiral aminophosphine ( S)-(−)-diphenyl-phenylethylaminophosphine affords the diastereomeric phosphonate complexes ( R, S) Co, S C-Cp ★CoI(P(0)(OMe) 2)(PPh 2NHC ★H(Me)Ph) ( 10a,10b) via Arbuzov dealkylation. 10a,10b are separable and configurationally stable in solution for extended periods. The structure and absolute configuration of the lower R f diastereomer (−)- 436- 10b were determined via single-crystal X-ray diffraction. It crystallizes as a toluene solvate in space group P2 1 with a 13.194(6), b 9.062(4), c 17.023(5) Å, β 108.78(3)°, Z = 2, and was refined to R = 0.067 for 6318 reflections. Spectroscopic and structural evidence demonstrate a strong 1,6 intramolecular NH ⋯ OP hydrogen bond between the aminophosphine NH and the basic phosphoryl oxygen, which establishes a quasi-boat conformation. Proton nuclear Overhauser difference spectra show that the conformation in solution is the same as that observed in the solid state.

ChemInform Abstract: A New Synthesis of Rhenium‐Carbene Complexes from the Reaction of Cp(CO)2ReH‐ with Cp2Zr(η2‐COR)Cl.

AbstractThe preparation of the new title complexes (III) is followed by 1H NMR spectroscopy.

Reaktivität der Metall-Metall-Mehrfachbindung in Übergangsmetall-Komplexen: XIV. Reaktion von Cp *2CoRh(μ-CO) 2 (Cp * = η 5-C 5Me 5) mit Schwefel oder Selen und Molkülstruktur von Cp *2CoRh(CO) 2(μ-Se) 2

The reaction of Cp * 2CoRh(μ-CO) 2 ( M M; Cp * = η 5-C 5Me 5) with elemental sulfur or selenium gives the complexes Cp * 2CoRhS 8 and Cp * 2CoRhSe 5, both are distinguished by a high chalcogen content. The only CO containing intermediate product Cp * 2CoRh(CO) 2Se 2 that was isolated has been characterized by an X-ray diffraction study. The compound contains a rhombohedric, planar M 2E 2 four-membered ring (angle CoSeRh 101.3(1)°) bonded to anti-oriented Cp * and CO ligands. Other CO-containing intermediates can be detected only spectroscopically. Thus the Co atom in the MM double bond exerts an accelerating influence on the reaction rate when compared to Rh.

A new synthesis of rhenium-carbene complexes from the reaction of Cp(CO)2ReH- with Cp2Zr(.eta.2-COR)Cl

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA new synthesis of rhenium-carbene complexes from the reaction of Cp(CO)2ReH- with Cp2Zr(.eta.2-COR)ClCharles P. Casey and Hideo NagashimaCite this: J. Am. Chem. Soc. 1989, 111, 6, 2352–2353Publication Date (Print):March 1, 1989Publication History Published online1 May 2002Published inissue 1 March 1989https://doi.org/10.1021/ja00188a088RIGHTS & PERMISSIONSArticle Views221Altmetric-Citations14LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (305 KB) Get e-Alerts Get e-Alerts

Oxidative Addition von Thiolen an Stibinidenkomplexe

The stibinidene complex [Cp′(CO) 2Mn] 2SbSPh ( 1 (Cp′ = η 5CH 3C 5H 4) could not be obtained from the reaction of the iodostibinidene complex [Cp′(CO) 2Mn] 2SbI ( 2) with thiophenol. Instead, 2 reacts with thiophenol to give the product of an oxidative addition process, Cp′(CO) 2MnSb(SPh) 3 ( 3) and the radical complex, Cp′(CO) 2MnSPh ( 4). The compounds 3 and 4 could also be obtained from the reaction of Cp′(CO) 2MnTHF with Sb(SPh) 3. The structure of 3 has been determined by X-ray crystallography.