U¨bergangsmetall—Carbin—Komplexe: LXIV. Von equatorialen,zweikernigen silylcarben-komplexen des rheniumsU¨ber einen neuartigen kationischen silylcarbin-komplex zu axialen carben-komplexen

Decacarbonyldirhenium reacts with LiSi(C₆H₅)₃ to yield, on subsequent alkylation with FCH₃SO₃ or (C₂H₅)₃OBF₄, the equatorial nonacarbonyl[triphenylsily(alkoxy)carbene] dirhenium complexeseq-(CO)₉Re₂C(OR)Si(C₆H₅)₃(Ia, R - CH₃; Ib, R - C₄H₈OCH₃; Ic. R - C₂H₅). Reactions of these compounds with Al₂Cl₆ or Al₂Br₆ produce novel binuclear, cationic silycarbyne complexes, ax-[(CO)₉Re₂CSi(C₆H₅)₃]⁺ AlX₄^- (IIa, X - Cl; IIb, X - Br). Treatment of these complexes with alcohols results in formation of the axial nonacarbonyl(carbene)dirhenium complexesax-(CO)₉Re₂C(OR)Si(C₆H₅)₃ (IIIa, R - CH₃; IIIb, R - C₂H₅). The isomeric carbene complexes Ia and IIIa react with dialkylamine affording the isomeric aminocarbene complexeseq-(CO)₉Re₂C(CH₃)₂]-Si(C₆H₅)₃ (V) andax-(CO)₉Re₂Cl(NR₂)Si(C₆H₅)₃ (IVa, R - CH₃; IVb, R - C₂H₅). Reaction conditions, properties and spectroscopic data of the new compounds are reported.     

Isocyanide addition to MN2(CO)5(Ph2PCH2PPh2)2 and the formation of a four-electron doubly-bridging isocyanide

The reactions of Fe(CO)₅, Fe(CO)₄P(C₆H₅)₃, M(CO)₆ (M  W, Mo, Cr), and (CH₃C₅H₄Mn(CO)₃ with KH and several boron and aluminium hydrides were investigated. Iron pentacarbonyl was converted quantitatively to K⁺Fe(CO)₄-(CHO) by hydride transfer from KBH(OCH₃)₃ allowing isolation of [P(C₆H₅)₃]₂-Nⁿ⁺Fe(CO)₄(CHO)^? in 50% yield. Lower yields were obtained with LiBH(C₂H₅)₃, and other hydride sources gave little or no formyl product. The stability of Fe(CO)₄(CHO)^? in THP was found to depend on the cation, decreasing in the order [P(C₆H₅)₃]₂N⁺ > K⁺ > Na⁺ > Li⁺. No formyl complexes were isolated and no spectroscopic evidence for formyl formation was observed in the reactions of the other transition metal carbonyls with several hydride sources. Fe(CO)₄-P(C₆H₅)₃ gave K₂Fe(CO)₄ when treated with KHB(OCH₃)₃. When treated with LiBH(C₂H₅)₃, W(CO)₆ gave a mixture of HW₂(CO)₁₀^?and (OC)₅W(COC₂H₅)^?; the latter was methylated to give the carbene complex (OC)₅WC(OCH₃)C₂H₅.     

Acetoxythallation of dialkylacetylenes

The reaction of NaRe(CO)₅ with CH₃Mn(CO)₅ and with C₆H₅Mn(CO)₅ followed by alkylation with CH₃OSO₂F gives cis-(CO)₅ReMn(CO)₄C(OCH₃)CH₃ and cis-(CO)₅ReMn(CO)₄C(OCH₃)C₆H₅ respectively.     

Arene derivatives of molybdenum and tungsten Communication 1. Anisole tricarbonyl complexes of molybdenum and tungsten

Conclusions The reaction of anisole with the molybdenum and tungsten hexacarbonyls gave the previously unknown antsole complexes (C₆H₅OCH₃)M(CO)₃.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2090–2091, September, 1973.The authors express their gratitude to P. V. Petrovskii for assistance in taking and discussing the NMR spectra.     

Derivate des borabenzols: XVIII. Vanadium-komplexe Des 1-methyl- und 1-phenylborinat-ions

Six borabenzene derivatives of vanadium are described. Reaction of the alkali metal borinates M(C₅H₅BR) (M = Na, K; R = Me, Ph) with VCl₃ yields the paramagnetic, sandwich complexes V(C₅H₅BR)₂. Reaction with HgCl₂ and [Na{O(CH₂CH₂OCH₃)₂}₂][V(CO)₆] affords the tetracarbonyl compounds V(CO)₄(C₅H₅BR). Upon heating in cycloheptatriene, the latter compounds produce the paramagnetic cycloheptatrienyl complexes V(C₅H₅BR)(C₇H₇) with sandwich structures. An X-ray structural study of V(CO)₄(C₅H₅BMe) shows that the V(CO)₄ fragment in the crystal is rotated by 10.4° relative to an ideal, eclipsed conformation where two CO groups are present in the plane through the B, V and C(4) atoms.     

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.     

Basische metalle : IX. Synthese und kristallstruktur von C5H5Co(PMe3)CS2. Reaktionen zu zweikernkomplexen mit Co(SCS)Cr- und Co(SCS)Mn-Brückenbindungen

C₅H₅Co(PMe₃)CS₂ (IV) is formed in practically quantitative yield in the reaction of C₅H₅Co(PMe₃)₂ (I) or the heterobinuclear complex C₅H₅(PMe₃)Co(CO)₂Mn(CO)C₅H₄Me (III) with CS₂. The crystal structure shows that the carbon disulfide bonds as a dihapto ligand through the carbon and one sulfur atom (S(2)) (CoC = 1.89, CoS(2) = 2.24 Å, S(2)CS(1) = 141.2°). The two CS bond lengths in IV (CS(2) = 1.68, CS(1) =1.60 Å) are greater than in free CS₂ (1.554Å) which is in agreement with the strong π-acceptor character of h²-CS₂ as shown in the spectroscopic data. IV reacts with Cr(CO)₅THF and C₅H₅Mn(CO)₂THF to give the complexes C₅H₅(PMe₃)Co(SCS)Cr(CO)₅ (V) and C₅H₅(PMe₃)Co(SCS)Mn(CO)₂C₅H₅ (VI) respectively, in which the sulfur atom S(1) that is not bound to cobalt coordinates to the 16-electron fragments Cr(CO)₅ and Mn(CO)₂C₅H₅. The spectroscopic data of IV, V and VI are discussed.     

Reactions of metal carbonyl derivatives : XIII. Reaction of bis[μ-(tert-butylsulphido)tricarbonyl-iron] with tertiary and ditertiary phosphines and phosphites

The ligands L  P(C₂H₅)₃, P(C₆H₅)₃, P(OCH₃)₃ and P(OC₆H₅)₃ react with [Fe(CO)₃(S-t-C₄H₉)]₂ to give mono-substituted Fe₂(CO)₅L(S-t-C₄H₉)₂ or bis-substituted [Fe(CO)₂L(S-t-C₄H₉)]₂ depending on the reaction conditions. With the exception of [Fe(CO)₂P(C₂H₅)₃(S-t-C₄H₉)]₂, the latter derivatives occur both in solution and in the solid state as a single isomer in which the ligands L are bonded trans to the metal-metal bond. Whereas an asymmetrically bis-substituted product, Fe(CO)₃(S-t-C₄H₉)₂Fe(CO)L' is formed in the reaction of [Fe(CO)₃(S-t-C₄H₉)]₂ with L' &2.dbnd; cis-(C₆H₅)₂PC₂H₂P(C₆H₅)₂, symmetrically bis-substituted derivatives [Fe(CO)₂(S-t-C₄H₉)]₂L', in which the ligand bridges the two iron atoms are produced in the corresponding reactions involving L'  (C₆H₅)₂P(CH_2nP(C₆H₅)₂ (n  1 and 2). The NMR spectrum of [Fe(CO)₂P(OCH₃)₃(S-t-C₄H₉)]₂, as well as those of the complexes [Fe(CO)₂P(OCH₃)₃SR]₂ (R  CH₃ and i-C₃H₇) which have also been synthesised in this study, is interpreted in terms of a virtual coupling effect.     

Reaktionen von komplexliganden XXXVIII. Bisacylierung von aminocarben-komplexen zu 2-azaallenyl-komplexen

The DMAP (4-N,N-dimethylaminopyridine) catalyzed bisacylation of pentacarbonyl(amino)carbenechromium complexes affords a high-yield access to 2-azaallenyl complexes as exemplified by (CO)₅CrC(p-CH₃C₆H₄)NC(^tBu)(O₂C^tBu), the crystal structure of which has been determined by X-ray diffraction.     

X-ray analysis of 1,3-dioxa-6-aza-2-silacyclooctane derivatives

X-ray analysis has been conducted on four dioxaazasilacyclooctanes R₂Si(OCH₂CH₂)₂NR′ with R = C₆H₅, R′ = CH₃ (IV); R = C₆H₅, R′ = (CH₃)₃C (V); R = CH₃, R′ = C₆H₅ (VI) and R = R′ = C₆H₅ (VII). The interatomic distances SiN measured for these compounds had the values: 2.68 (IV), 3.16 (V), 3.19 (VI) and 3.08 Å (VII), indicating weak nitrogen—silicon interaction and a virtual lack of coordinate Si ← N bonding. The data of other authors and our own evidence suggest that the Si ← N interaction in these compounds is strongly influenced by the electronic effects of Si- and N-substituents and, in particular, by the steric effects of the latter.     

Photochemical and thermal reactions of η5-cyclopentadienyltetracarbonylvanadium and bis(pentafluorophenyl)acetylene

The photolysis of (η⁵-C₅H₅)V(CO)₄ in the presence of one or two equivalents of bis(pentafluorophenyl)acetylene yields (η⁵-C₅H₅)V(CO)₂(C₆F₅CCC₆F₅). One carbon monoxide ligand in this acetylene adduct can be photochemically displaced by triphenylphosphine to yield (η⁵-C₅H₅)V(CO)[P(C₆H₅)₃](C₆F₅CCC₆F₅). This complex is also obtained by the photolysis of (η⁵-C₅H₅)V(CO)₃P(C₆H₅)₃ in the presence of bis(pentafluorophenyl)acetylene. In vacuo, melt-phase thermolysis of (η⁵-C₅H₅)V(CO)₂(C₆F₅CCC₆F₅) and bis(pentafluorophenyl)acetylene produces (η⁵-C₅H₅)V(CO)(C₆F₅CCC₆F₅)₂. This diacetylenic complex as well as the perfluorinated organic compounds 2,3,5,6-tetrakis(pentafluorophenyl)-1,4-benzoquinone, 2,3,4,5-tetrakis(pentafluorophenyl)cyclopentadienone and 2,3,4,5,6,7-hexakis(pentafluorophenyl)cycloheptatrienone are also obtained from thermal reactions of (η⁵-C₅H₅)V(CO)₄ and bis(pentafluorophenyl)acetylene in solution. Photolysis of (η⁵-C₅H₅)V(CO)(C₆F₅CCC₆F₅)₂ in the presence of carbon monoxide produces (η⁵-C₅H₅)V(CO)₂(C₆F₅CCC₆F₅). The photochemical and thermal reactions of bis(pentafluorophenyl)acetylene and (η⁵-C₅H₅)V(CO)₄ are compared and contrasted with similar reactions of diphenylacetylene and (η⁵-C₅H₅)V(CO)₄.     

Protonation and methylation of η4-2,3,5,6-tetramethyl-1,4-benzoquinone(η5-pentamethylcyclopentadienyl)cobalt

The preparation of the η⁴-4-2,3,5,6-tetramethyl-1,4-benzoquinonecomplex [CO(C₅Me₅)(C₁₀H₁₂O₂)] (I) is reported. Complex I undergoesreversible protonation to yield the 2-6-η-4-hydroxy-1-oxo-2,3,5,6-tetramethylcyclohexadienyl complex [Co(C₅Me₅)(C₁₀H₁₃O₂)BF₄ (II) and diprotonation to yield the η⁶-6-1,4-dihydroxy-2,3,5,6-tetramethylbenzene complex [Co(C₅Me₅)(C₁₀H₁₄O₂)] (BF₄)₂ (III). Methylation of complex I with MeI/AgPF₆ gives the 26-η-4-methoxy-1-oxo-2,3,5,6-tetramethylcyclohexadienyl complex [Co(C₅Me₅)(C₁₁H₁₅O₂])PF₆ (IV). In trifluoroacetic acid solution complex IV is protonated to form the η⁶-1-hydroxy-4-methoxy-2,3,5,6-tetramethylbenzene cation [Co(C₅Me₅)-(C₁₁H₁₆O₂)]²⁺     

Unusual route to and rearrangement of four-membered ring complexes C5H5Fe (CO) [ (C6H5)2PN(R)CH (C6H5) ]

The amine substituted phosphines (C₆H₅)₂PN(H)CH₂CH₃ and (C₆H₅)₂PN(H)CH₂C₆H₅ react with C₅H₅Fe(CO)₂CH(C₆H₅) (OCH₃) photolytically to give moderate yields of the four-membered chelate ring complexes C₅H₅$\text{Fe (CO) [(C}{}_6\text{H}{}_5\text{)}{}_2\text{PN (CH}{}_2\text{CH}{}_3\text{) C}$H (C₆H₅)] and C₅H₅$\text{Fe (CO) [(C}{}_6\text{H}{}_5\text{)}{}_2\text{PN (CH}{}_2\text{C}{}_6\text{H}{}_5\text{)C}$H(C₆H₅)], respectively. Photolysis of C₅H₅Fe(CO)₂CH(C₆H₅) (OCH₃) in the presence of (S)-(?)-diphenyl(1-phenylethylamino)phosphine leads to the isolation of C₅H₅Fe(CO)[(C₆H₅)2PNC(CH₃) (C₆H₅)]CH₂C₆H₅ which is proposed to arise from a formally 1,3-hydrogen shift rearrangement of an intermediate four-membered chelate ring complex.     

The 31P NMR spectra of ArCr(CO)2P(C6H5)3 compounds in neutral and acidic media

The ³¹P NMR spectra of C₆H₅XCr(CO)₂P(C₆H₅)₃ (X = H, CH₃, OCH₃, N(CH₃)₂, COOCH₃) (I), p-C₆H₄X₂Cr(CO)₂P(C₆H₅)₃ (X = COOCH₃)(II) and C₆H₃X₃Cr(CO)₂P(C₆H₅)₃ (X = CH₃) (III) complexes in neutral and acidic media were investigated. The protonation of complexes I and III in trifluoroacetic acid results in the greater upfield shielding of ³¹P{¹H} signal. In this case the complexes I (X = H, CH₃, OCH₃) are completely protonated at the metal, complex I (X = COOCH₃)is partially protonated, while no protonation occurs in the case of complex II.Temperature-dependence of the ³¹P{¹H} NMR spectra was investigated for complexes I (X = H, OCH₃) in a 1/10 mixture of trifluoroacetic acid and toluene and for complexes I (X = COOCH₃) and II in trifluoroacetic acid. The degree of protonation was found to increase with decreasing temperature.     

Beiträge zur Organolanthanidchemie. III [1]. Darstellung und Eigenschaften von 1,4-Diaryl-1,3-butadien-Komplexen der Lanthanide

Contributions to Organolanthanide Chemistry. III. Synthesis and Properties of 1,4-Diaryl-1,3-butadiene Lanthanide Complexes Cyclopentadienyllanthanide halides react with 1,4-diarylbutadienes in the presence of alkali metals to give Cp*La(1,4-Ph₂C₄H₄) · DME ( I ), Cp*La(1,4-{o-CH₃O? C₆H₄}₂ · C₄H₄) · 2DME ( II ), [Li(THF)₃][Sm(1,4-Ph₂C₄H₄)₂] ( III ), [Li(DME)][(1,4-{p-CH₃? C₆H₄}₂C₄H₄)LuCl₂] ( IV ) and [Li(DME)][(1,4-{o-CH₃O? C₆H₄}₂C₄H₄)LuCl₂] ( V ). Samariumtrichloride reacts with 1,4-diphenyl-butadiene and lithium in tetrahydrofurane with formation of [Li(THF)₄][Sm(1,4-Ph₂C₄H₄)₂] ( VI ). Reaction of samarium with the p-tolyl derivative in the presence of iodine gives (1,4-{p-CH₃? C₆H₄}₂C₄H₄)SmI · 3THF ( VII ). The compounds were characterized by elementary analysis, i.r., ¹H- and ¹³C- n.m.r., and EI-MS spectra.     

Protonation and methylation of η-2,3,5,6-tetramethyl-1,4-benzoquinone(η-pentamethylcyclopentadienyl)cobalt

The preparation of the η⁴-4-2,3,5,6-tetramethyl-1,4-benzoquinonecomplex [CO(C₅Me₅)(C₁₀H₁₂O₂)] (I) is reported. Complex I undergoesreversible protonation to yield the 2-6-η-4-hydroxy-1-oxo-2,3,5,6-tetramethylcyclohexadienyl complex [Co(C₅Me₅)(C₁₀H₁₃O₂)BF₄ (II) and diprotonation to yield the η⁶-6-1,4-dihydroxy-2,3,5,6-tetramethylbenzene complex [Co(C₅Me₅)(C₁₀H₁₄O₂)] (BF₄)₂ (III). Methylation of complex I with MeI/AgPF₆ gives the 2---6-η-4-methoxy-1-oxo-2,3,5,6-tetramethylcyclohexadienyl complex [Co(C₅Me₅)(C₁₁H₁₅O₂])PF₆ (IV). In trifluoroacetic acid solution complex IV is protonated to form the η⁶-1-hydroxy-4-methoxy-2,3,5,6-tetramethylbenzene cation [Co(C₅Me₅)-(C₁₁H₁₆O₂)]²⁺     

Insertion reactions of isocyanides with platinumcarbon σ-bonded complexes

[Pt(C₁₀H₁₂OCH₃)(PPh₃)Cl] reacts readily with isocyanides by displacement of the coordinated olefinic end of the organic moiety followed by insertion of the isocyanide into the metalcarbon σ-bond. The reaction between the methoxydienyl complex [Pt(C₁₀H₁₂OCH₃)Cl]₂ and cyclohexyl isocyanide involves chloride bridge-splitting to give [Pt(C₁₀H₁₂OCH₃)(C₆H₁₁NC)Cl], followed by olefin displacement and finally isocyanide insertion. The imino derivative produced in this latter reaction has a trans-isocyanide configuration.The chemical properties of these new isocyanide complexes are discussed in terms of relative trans influences, coordinating abilities, and electrophilic characters in comparison with the CO analogues.     

The first synthesis of dihydro-3H-pyrido[2,3-b][1,4]diazepinols and a new alternative approach for diazepinone analogues

The first synthesis of a series of 2-aryl(heteroaryl)-4-trifluoromethyl-4,5-dihydro-3H-pyrido[2,3-b][1,4]diazepin-4-ols, where aryl = C₆H₅, 4-FC₆H₄, 4-ClC₆H₄, 4-BrC₆H₄, 4-CH₃C₆H₄, 4-OCH₃C₆H₄, 4,4′-biphenyl, 1-naphthyl and heteroaryl = 2-thienyl, 2-furyl obtained from the direct cyclocondensation reaction of 4-methoxy-1,1,1-trifluoroalk-3-en-2-ones with 2,3-diaminopyridine in 54-71% yield, is reported. Another alternative and efficient route for the synthesis of a series of 2-aryl(heteroaryl)-3H-pyrido[2,3-b][1,4]diazepin-4(5H)-ones from the reaction 4-methoxy-1,1,1-trichloroalk-3-en-2-ones with 2,3-diaminopyridine, in 54-70% yield, is also reported.     

Tripeldecker-komplexe: III. Komplexierungsreaktionen von 1-phenyl-4,5-dihydroborepin unter gerüstumlagerung. Synthese und struktur von tripeldecker-komplexen des mangans und des eisens mit 2-ethyl-1-phenylborol als brückenligand

The thermal reaction of 1-phenyl-4,5-dihydroborepin (I) with Mn₂(CO)₁₀ produces the triple-decked complex (OC)₃Mn(μ-L)Mn(CO)₃ (III) where L is 2-ethyl-1-phenylborole. The analogous system I/[(C₅H₅)Fe(CO)₂]₂ inter alia yields the triple-decked sandwich complex (C₅H₅)Fe(μ-L)Fe(C₅H₅) (VI) and the borabenzene derivative (C₅H₅)Fe(2-CH₃C₅H₄BC₆H₅) (VIII). The structures of the 30-electron compounds III and VI have been determined by X-ray analyses.     

The preparation and properties of metallofluorene complexes of transition metals.

Metalluorene complexes (π-C₅H₅)M(CO)(C₁₂H₈) (IVa)-(IVc) and (π-C₅H₅) (CO)(C₁₂F₈) (IVd)-(IVf) (M = Co, Rh and Ir) have been prepared from reactions of the appropriate (π-cyclopentadienyl) carbonylmetal diiodides with 2,2′-dilithhiolbiphenyl (IIa) and 2,2′-dilithiooctafluorobiphenyl (IIb), respectively The triphenylphoshine substitution reactions of cobalt compounds (IVa) and (IVd) have also been studied. Reaction of (IIa) and (IIb) with norbornadieneplatinum dichloride result in the preparation of metallocyclic platinum compounds (π-C₇H₈) and (π-C₇H₈)Pt(C₁₂H₈). A reaction of (IIb) with zirconocene dichloride produces (π-C₅H₅)₂Zr(C₁₂F₈), the first example of a ziconium-containing metalofluorene.