Synthesis of chloro-carbonyl derivatives of rhenium,ruthenium, rhodium,iridium and platinum via reaction of the metal atoms with oxalyl chloride

Co-condensation of atoms of Re, Ru, Rh, Ir and Pt with oxalyl chloride gives metal chloro-carbonyl derivatives which may be used as precursors to the compounds [Re(CO)₄Cl]₂, [Ru(PMe₃)₃(CO)Cl₂], α-[Ru(CO)₃Cl(μ-Cl)]₂, [Ru(PPh₃)₂(CO)₂Cl₂], [Rh(CO)₂(μ-Cl)]₂, [Rh(PPh₃)₂COCl], [Ir(PPh₃)(CO)₂Cl₃] and cis-Pt(CO)₂Cl₂. Molybdenum atoms with oxalyl chloride give molybdenum-chloro derivatives.     

过渡金属钌、铑配合物在室温离子液体中催化硅氢加成反应的研究

研究了在室温离子液体以及室温离子液体/有机溶剂复合介质体系中, Rh(PPh₃)₃Cl, Ru(PPh₃)₃Cl₂等催化烯烃与三乙氧基硅烷的硅氢加成反应. 实验结果表明, 在乙二醇二甲醚/离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMImBF₆) (V/V＝1/4)介质中, 于90 ℃下, 己烯与三乙氧基硅烷反应的转化率为100%, β加成物的选择性可达89.0%. 而用Rh(PPh₃)₃Cl作为反应的催化剂, 在纯离子液体BMImPF₆中, 就可以高效催化烯烃与三乙氧基氢硅烷的加成反应. 过渡金属Rh(PPh₃)₃Cl, Ru(PPh₃)₃Cl₂催化剂/离子液体BMImPF₆催化体系, 不仅解决了产物与催化剂分离困难这一难题, 同时, 离子液体BMImPF₆的存在提高了过渡金属Rh(PPh₃)₃Cl, Ru(PPh₃)₃Cl₂催化硅氢加成反应的活性, 特别是β加成物的选择性. 反应结束后, 催化剂/离子液体与产物易于分离, 并且可以重复使用.     

Complexing behaviour ofN-phenylcarbamoylpyrrole-2-thiocarboxamide

Summary The complexes Pd(PTH)₂Cl₂ · 3.5 H₂O, Pd(PTH)₃(PPh₃), Ru(PTH)₂(PPh₃)Cl₂, Ru(PTH)₂(PPh₃)Cl₃, Rh(PTH)₂(PPh₃)Cl and Rh(PT)Cl₂ · 0.5 H₂O, where PTH isN-phenylcarbamoylpyrrole-2-thiocarboxamide, have been prepared and characterised by magnetic and spectral (i.r., u.v. and visible) studies.     

Synthesis and characterization of transition metal complexes of a new bidentate ligand {2-(diphenylphosphino)ethyl}benzylamine

A new bidentate ligand {2-(diphenylphosphino)ethyl}benzylamine(DPEBA) was synthesized and characterized based on the IR, mass and ¹H, ¹³C and ³¹P NMR spectra. Various complexes of platinum group metal ions and Ni(II) and Co(II) ions with the ligand were synthesized. Reaction of RuCl₂(PPh₃)₃ or RuCl₂(Me₂SO)₄ with the ligand DPEBA, resulted in formation of a penta-coordinate, Ru(II) species of the composition [RuCl(DPEBA)₂]Cl. Carbonylation of [RuCl(DPEBA)₂]Cl gave an octahedral carbonyl complex of the type [RuCl(CO)(DPEBA)₂]Cl. The reaction of RuCl₃·3H₂O or RuCl₃(AsPh₃)₂MeOH with a twofold excess of the ligand gave an octahedral Ru(III) cationic species [Ru(DPEBA)₂Cl₂]Cl. Carbonylation of the Ru(III) complex gave rise to a carbonyl complex [RuCl(CO)(DPEBA)₂]Cl₂. The ligand DPEBA reacts with cobalt(II) chloride in methanol to give the 1 : 1 complex [Co(DPEBA)Cl₂]. A series of Rh(I) complexes [Rh(DPEBA)₂Cl], [ RhCl(CO)(DPEBA)] and [Rh(DPEBA)₂]Cl were synthesized by the reaction of DPEBA with RhCl(PPh₃)₃, RhCl(CO)(PPh₃)₂ and [Rh(COD)Cl]₂, respectively. Reaction of [Ir(COD)Cl]₂ and IrCl(CO)(PPh₃)₂ with the ligand DPEBA, gave the square-planar complexes [Ir(DPBA)₂]Cl and [Ir(DPEBA)(CO)Cl], respectively. Octahedral cationic complexes of the type [M(DPEBA)₂Cl₂]Cl (M = Rh(III), Ir(III)) were synthesized by the reaction of the ligand DPEBA and rhodium and iridium trichlorides. Reaction of NiCl₂·6H₂O with DPEBA in 1 : 2 molar equivalents, in boiling butanol gave an octahedral neutral complex [Ni(DPEBA)₂Cl₂] which readily rearranges to the square-planar complex [Ni(DPEBA)₂]Cl₂ in methanol. Reaction of Pd(II) and Pt(II) chlorides with DPEBA gave square-planar, cationic complexes of the type [M(DPEBA)₂Cl]Cl (M = Pd, Pt). All the complexes were characterized on the basis of their analytical and spectral data.     

The catalytic transformation of nitrosobenzene into azoxy and azobenzene

Nitrosobenzene is converted into azoxybenzene in alcoholic media in the presence of Ru(CO)₃(PPh₃)₂ as catalyst and under an inert atmosphere; Fe(CO)₃(PPh₃)₂ and palladium complexes such as PdL₂Cl₂ (L  PhNO, p-MeC₆H₄NH₂, PPh₃) and Pd₃(CO)₃(PPh₃)₄, are less active as catalysts. Under CO pressure and with Ru(CO)₃(PPh₃)₂ as catalyst, nitrosobenzene is converted into azobenzene and aniline, while azoxybenzene gives azobenzene.     

Activation of thiocyanogen and selenocyanogen by low oxidation state transition metal complexes

Thiocyanogen and selenocyanogen react with Ru(CO)₃(PPh₃)₂ to give respectively the complexes Ru(CO)₂(PPh₃)₂(NCS)₂ and Ru(CO)₂(PPh₃)₂(NCSe)₂. (M—NCS and M—SCN represent N- and S-thiocyanato groups, M—NCSe and M—SeCN represent N- and Se-selenocyanato groups respectively, while M—CNS indicates the bridging coordination mode of thiocyanate.) Only the thiocyanogen reacts with Ru₃(CO)₁₂ giving [Ru(CO)₂(CNS)₂]_n, which dissolves in hot coordinating solvents, such as pyridine, to form Ru(CO)₂(py)₂(NCS)₂. Selenocyanogen is less effective than thiocyanogen in the oxidative addition reactions with rhodium(I) and iridium(I) complexes; in fact selenocyanogen does not react with Rh(CO)(PPh₃)₂Cl while with Ir(CO)(PPh₃)₂Cl the former gives Ir(CO)(PPh₃)₂(SeCN)₂Cl by an equilibrium reaction. The coordination number of the metal and the charge on the complex do not change the bonding mode of the thiocyanate and selenocyanate groups in the iridium(III) complexes; in the Ir(PPh₃)₂ClX₂ and [Ir(Ph₂PC₂H₄PPh₂)₂X₂]⁺ (X = SCN and SeCN) complexes the pseudohalogens are S- and Se-bonded.The complexes trans-M(PPh₃)₂(SeCN)₂ (M = Pd, Pt) have been obtained by reacting M(PPh₃)₄ with selenocyanogen.     

Derivate des borols: IX. (η5-borol)metall-komplexe von ruthenium,osmium und rhodium

Dehydrogenating complexation of borolenes with carbonyls (Ru₃(CO)₁₂, Os₃(CO)₁₂), Wilkinson's catalyst (RhCl(PPh₃)₃) and related compounds (RuCl₂(PPh₃)₃, RuHCl(PPh₃)₃, OSCl₂(PPh₃)₃), and (η⁶-arene)ruthenium complexes (Ru(η-C₆H₆)(η⁴-C₆H₈), [Ru(η-C₆H₆)Cl₂]₂, [Ru(η-C₆-Me₆)Cl₂]₂) leads to the (η⁵-borole)metal complexes of Ru, Os, and Rh. Inter alia, the preparation of the complexes Ru(CO)₃(η⁵-C₄H₄BF) (R = Ph, OMe, Me), Os(CO)₃L (L = η⁵-C₄H₄BPh), MHClL(PPh₃)₂ (M = Ru, Os), RhClL(PPh₃)₂, and RuL(η-C₆R₆) (R = H, Me) is described. The structures of RuHClL(PPh₃)₂ and RhClL(PPh₃)₂ have been determined by X-ray diffraction analysis.     

Reactions of cationic rhodium(I) carbonyl compounds with nucleophiles to form alkoxo,carboalkoxy and carboxylato complexes. Part II

Summary The rhodium(I) carbonyl compounds [Rh(CO)L₂2] [BF₄]. 1/2CH₂Cl_nn2 (L = PPh₂ or AsPh₃) react with the nucleophiles OMe⁻, RCOO⁻ (R = Me, Et) under nitrogen to form [Rh(OR)(CO)L₂] (1)–(2) and [Rh(OOCR)(CO)L₂] (7)–(₁₀), respectively. Addition of [Rh(CO)₂(PPh₃)₂]-[BF ₄] to OMe⁻ under nitrogen produces [Rh(COOMe)-(CO) (PPh₃)₂]-MeOH (3), whilst reactions of [Rh(CO)-(PPh₃)₂] [BF₄]·1/2CH₂Cl₂ and [Rh(CO)₂(PPh₃)₂] [BF₄] with OR_- (R = Me, Et or n-Pr) in the presence of CO produce [Rh(COOR)(CO)₂(PPh₃)₂] (4)–(6). The products have been characterised by i.r., ¹H, ³¹P, ¹³Cn.m.r. spectroscopy and elemental analysis.     

The reaction of formyl fluoride with transition metal complexes

Formyl fluoride reacts with metal carbonyl anions in a manner similar to acetic formic anhydride. Although formyl complexes may have been formed as unstable intermediates, no neutral formyl complexes could be isolated but rather the expected decomposition products, the metal carbonyl hydrides or ?imers, were produced. The attempted oxidative addition of formyl fluoride to various coordinately unsaturated metal complexes also did not result in the formation of formyl derivatives. HF adducts were obtained from the reaction ?fIr(CO)Cl(PR₃)₂ or M(PPh₃)₄ (M Pt or Pd) with formyl fluoride whereas Ru(NO)Cl(PPh₃)₂ and Rh(PPh₃)₃ Cl give the CO complexes Ru(NO)(CO)Cl(PPh₃)₂ and Rh(CO)Cl(PPh₃)₂, respectively.     

Reaction of alkenyl carbonyl ruthenium(II) complexes with t-butyl isocyanide. Synthesis of η1-acylruthenium(II) complexes by intramolecular CO insertion

Reaction of Ru(CO)Cl(CHCHR)(PPh₃)₂ or Ru(CO)Cl(CHCHR)(PPh₃)₂L (L = py, Me₂Hpz) with 1 equivalent of t-butyl isocyanide gives the alkenyl derivatives Ru(CO)Cl(CHCHR)(PPh₃)₂(t-BuNC). When an excess of isocyanide is used, further reaction results in intramolecular CO insertion to yield η¹-acyl complexes [Ru(COCHCHR) (t-BuNC)₃(PPh₃)₂]Cl. Related complexes were obtained from [Ru(CO)(CHCHR)(MeCN)₂(PPh₃)₂]PF₆ and an excess of isocyanide.     

Synthesis,characterization and anticancer activity of 3-aminopyrazine-2-carboxylic acid transition metal complexes

Synthetic procedures are described that allow access to the new complexes cis-[Mo₂O₅(apc)₂], cis-[WO₂(apc)₂], trans-[UO₂(apc)₂], [Ru(apc)₂(H₂O)₂], [Ru(PPh₃)₂(apc)₂], [Rh(apc)₃], [Rh(PPh₃)₂(apc)₂]ClO₄, [M(apc)₂], [M(PPh₃)₂(apc)]Cl, [M(bpy)(apc)]Cl (M(II) = Pd, Pt), [Pd(bpy)(apc)Cl], [Ag(apc)(H₂O)₂] and [Ir(bpy)(Hapc)₂]Cl₃, where Hapc, is 3-aminopyrazine-2-carboxylic acid. These complexes were characterized by physico-chemical and spectroscopic techniques. Both Hapc and several of its complexes display significant anticancer activity against Ehrlich ascites tumour cells (EAC) in albino mice.     

Nucleophilic Aromatic Addition Reactions of the Metallabenzenes and Metallapyridinium: Attacking Aromatic Metallacycles with Bis(diphenylphosphino)methane to Form Metallacyclohexadienes and Cyclic η2‐Allene‐Coordinated Complexes

The reactions of phosphonium‐substituted metallabenzenes and metallapyridinium with bis(diphenylphosphino)methane (DPPM) were investigated. Treatment of [Os{CHC(PPh₃)CHC(PPh₃)CH}Cl₂(PPh₃)₂]Cl with DPPM produced osmabenzenes [Os{CHC(PPh₃)CHC(PPh₃)CH}Cl₂{(PPh₂)CH₂(PPh₂)}]Cl ( 2 ), [Os{CHC(PPh₃)CHC(PPh₃)CH}Cl{(PPh₂)CH₂(PPh₂)}₂]Cl₂ ( 3 ), and cyclic osmium η²‐allene complex [Os{CH?C(PPh₃)CH?(η²‐C?CH)}Cl₂{(PPh₂)CH₂(PPh₂)}₂]Cl ( 4 ). When the analogue complex of osmabenzene 1 , ruthenabenzene [Ru{CHC(PPh₃)CHC(PPh₃)CH}Cl₂(PPh₃)₂]Cl, was used, the reaction produced ruthenacyclohexadiene [Ru{CH?C(PPh₃)CH?C(PPh₃)CH}Cl{(PPh₂)CH₂(PPh₂)}₂]Cl₂ ( 6 ), which could be viewed as a Jackson–Meisenheimer complex. Complex 6 is unstable in solution and can easily be convert to the cyclic ruthenium η²‐allene complexes [Ru{CH?C(PPh₃)CH?(η²‐C?CH)}Cl{(PPh₂)CH₂(PPh₂)}₂]Cl₂ ( 7 ) and [Ru{CH?C(PPh₃)CH?(η²‐C?CH)}Cl₂{(PPh₂)CH₂(PPh₂)}₂]Cl ( 8 ). The key intermediates of the reactions have been isolated and fully characterized, further supporting the proposed mechanism for the reactions. Similar reactions also occurred in phosphonium‐substituted metallapyridinium [OsCl₂{NHC(CH₃)C(Ph)C(PPh₃)CH}(PPh₃)₂]BF₄ to give the cyclic osmium η²‐allene‐imine complex [OsCl₂{NH?C(CH₃)C(Ph)?(η²‐C?CH)}{(PPh₂)CH₂(PPh₂)}(PPh₃)]BF₄ ( 11 ).     

Chemistry of a family of semiquinone monochelates of carbonyl ruthenium(II) generated by reacting quinones with hydridic species

The reactions of [Ru(H)(Cl)(CO)(PPh₃)₃] with 3,5-di-tert-butyl-o-benzoquinone (dbq) and 3,4,5,6-tetrachloro-o-benzoquinone (tcq) have afforded the corresponding semiquinone complexes [Ru^II(dbsq)(Cl)(CO)(PPh₃)₂] and [Ru^II(tcsq)(Cl)(CO)(PPh₃)₂], respectively. The reaction of [Ru(H)₂(CO)(PPh₃)₃] with tcq has furnished [Ru^II(tcsq)(H)(CO)(PPh₃)₂]. Structure determination of [Ru(dbsq)(Cl)(CO)(PPh₃)₂] has revealed that it is a model semiquinonoid chelate with two equal C---O lengths ( 1.291(6) and 1.296(6) Å). The complexes are one-electron paramagnetic (1.85μ_B) and their EPR spectra in fluid media display a triplet structure (g2.00) due to superhyperfine coupling with two trans-³¹P atoms (A_iso17 G). The stretching frequency of the CO ligand increases by 20 cm⁻¹ in going from [Ru(dbsq)(Cl)(CO)(PPh₃)₂] to [Ru(tcsq)(Cl)(CO)(PPh₃)₂] consistent with electron withdrawal by chloro substituents. For the same reason the E_1/2 values of the cyclic voltammetric quinone/semiquinone and semiquinone/catechol couples undergo a shift of 500 mV to higher potentials between [Ru(dbsq)(Cl)(CO)(PPh₃)₂] and [Ru(tcsq)(Cl)(CO)(PPh₃)₂].     

Reactions of 2-(arylazo)aniline with ruthenium substrates: Isolation, characterizations and reactivities of delocalized diazoketiminato and orthometallated Ru(II) chelates

Reactions of 2-(arylazo)aniline, HL-NH₂ [H represents the dissociable protons upon complexation and HL-NH₂ is p-RC₆H₄NNC₆H₄-NH₂; R = H for HL¹-NH₂; CH₃ for HL²-NH₂ and Cl for HL³-NH₂] with Ru(H)(CO)(PPh₃)₃Cl and Ru(CO)₃(PPh₃)₂ afforded products of compositions [(HL-NH)Ru(CO)Cl(PPh₃)₂] and [(L-NH)Ru(PPh₃)₂(CO)], respectively. All the complexes were characterized unequivocally. The X-ray structures of the complexes 4c and 5c have been determined. The cyclic volatammograms exhibited one reversible oxidative response in the range of 0.56–0.16 V versus SCE for [(L-NH)Ru(PPh₃)₂(CO)] and a quasi reversible oxidative response within 0.56–0.70 V versus SCE for [(HL-NH)Ru(CO)Cl(PPh₃)₂]. The conversion of ketones to corresponding alcohols has been studied in presence of newly synthesized ruthenium complexes.     

Rhodium(I) carbonyl complexes with sulphur and nitrogen donor ligands

Summary Rhodium(I) carbonyl complexes, namely [Rh(CO)₂ClL] where L = thiourea (Tu), 1,3-diphenyl-2-thiourea (DTu), dithizone (Dtz), indole (Id), 3-chloropyridine (Clpy), 3-hydroxypyridine (HOpy), 3-methylpyridine (Mepy), 2,5-dimethylpyridine (Me₂py) or 2,5-dichloropyridine (Cl₂py)] were prepared. [Rh(CO)₂Cl(Clpy)₂] has also been isolated. In the (Tu) complex, (C-S) occurs at ca. 710cm^-1, indicating the presence of a metal-sulphur bond. The carbonyl stretching frequencies in [Rh (CO)₂ClL] and [Rh(CO)₂CIL₂] occur at ca. 2100–1990 and 1830–1800 cm^-1, respectively. PPh₃ reacts with the complexes to form trans-[Rh(CO)Cl(PPh₃)₂]. The complexes were characterized by elemental analyses, conductivity measurements and by their i.r. spectra.     

Metallorganische lewissäuren: XXV. Übergangsmetallkomplexe mit o-koordiniertem perrhenat

The O-perrhenato complexes L_nMOReO₃ (L_nM = Re(CO)₅, Rh(PPh₃)₂(CO), Ir(PPh₃)₂(CO), Pt(PPh₃)₂(H), Ru(η⁵-C₅H₅)(PPh₃)₂, Os(PPh₃)₃(CO)(H), Ir(PPh₃)₂(CO)(H)(Cl) have been prepared from the corresponding halogeno compounds with AgReO₄ or NaReO₄, respectively. The spectroscopic data (IR, ¹H NMR) indicate that ReO₄⁻ is a stronger ligand compared to ClO₄⁻, SO₃CF₃⁻ and BF₄⁻.     

Platinum,iridium and rhodium complexes with substituted bis-(diphenylphosphino)methane ligands Ph2PCH(R)PPh2 (R = Me,Ph or SiMe3)

Substituted phosphines of the type Ph₂PCH(R)PPh₂ and their Pt^II complexes [PtX₂{Ph₂PCH(R)PPh₂}] (R = Me, Ph or SiMe₃; X = halide) were prepared. Treatment of [PtCl₂(NCBu^t)₂] with Ph₂PCH(SiMe₃)-PPh₂ gave [PtCl₂(Ph₂PCH₂PPh₂)], while treatment with Ph₂PCH(Ph)PPh₂ gave [Pt{Ph₂PCH(Ph)PPh₂}₂]Cl₂. Reaction of p-MeC₆H₄C≡CLi or PhC≡CLi with [PtX₂{Ph₂PCH(Me)PPh₂}] gave [Pt(C≡CC₆H₄Me-p)₂-{Ph₂PCH(Me)PPh₂}] (X = I) and [Pt{Ph₂PC(Me)PPh₂}₂](X = Cl),while reaction of p-MeC₆H₄C≡CLi with [Pt{Ph₂PCH(Ph)PPh₂}₂]Cl₂ gave [Pt{Ph₂PC(Ph)PPh₂}₂]. The platinum complexes [PtMe₂(dpmMe)] or [Pt(CH₂)₄(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph₂PCH(Me)PPh₂]. Treatment of [Ir(CO)Cl(PPh₃)₂] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)₂]Cl. The PF₆ salt was also prepared. Treatment of [Ir(CO)(dpmMe)₂]Cl with [Cu(C≡CPh)₂], [AgCl(PPh₃)] or [AuCl(PPh₃)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh₂(CO)₃(μ-Cl)(dpmMe)₂]BPh₄ using a procedure similar to that employed for an analogous dpm (dpm = Ph₂PCH₂PPh₂) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)₂]BPh₄ was obtained. The corresponding chloride and PF₆ salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)₂]Cl in CHCl₃ gave [RhHCl(dpmMe)₂]Cl. Recrystallization of [Rh(CO)(dpmMe)₂]BPh₄ from CHCl₃/EtOH gave [RhO₂(dpmMe)₂]BPh₄. Treatment of [Rh(CO)₂Cl₂]₂ with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)₂]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh₂(CO)₂(μ-Cl)(μ-CO)(dpmMe)₂]Cl and [Rh₂(CO)₂-(μ-Cl)(dpmMe)₂]Cl. This revised version was published online in June 2006 with corrections to the Cover Date.     

Syntheses,characterization, and crystal structures of ruthenium(II)/(III) complexes with tridentate salicylaldiminato ligands

Treatment of [Ru(PPh₃)₃Cl₂] with one equivalent of tridentate Schiff base 2-[(2-dimethylamino-ethylimino)-methyl]-phenol (HL) in the presence of triethylamine afforded a ruthenium(III) complex [RuCl₃(κ²-N,N-NH₂CH₂CH₂NMe₂)(PPh₃)] as a result of decomposition of HL. Interaction of HL and one equivalent of [RuHCl(CO)(PPh₃)₃], [Ru(CO)₂Cl₂] or [Ru(tht)₄Cl₂] (tht = tetrahydrothiophene) under different conditions led to isolation of the corresponding ruthenium(II) complexes [RuCl(κ³-N,N,O-L)(CO)(PPh₃)] (2), [RuCl(κ³-N,N,O-L)(CO)₂] (3), and a ruthenium(III) complex [RuCl₂(κ³-N,N,O-L)(tht)] (4), respectively. Molecular structures of 1·CH₂Cl₂, 2·CH₂Cl₂, 3 and 4 have been determined by single-crystal X-ray diffraction.     

Reactions involving transition metals: XX. A comparison of the reactions of 1,2,3,4,7,7-hexafluorobicyclo[2.2.1]heptadiene,and 2,3-bis(trimethyltin)- and 2,3-dichloro-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-dienes with low valent transition metal complexes

1,2,3,4,7,7-Hexafluorobicyclo[2.2.1]heptadiene (1) and 2,3-bis(trimethyltin)-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-diene (2) react with [M(Ph₃P)₄] (M = Pt, Pd) to afford air-stable adducts. 2,3-Dichloro-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-diene (3) gives only [PtCl₂(PPh₃)₂] with [Pt(Ph₃P)₄], but a low yield of an adduct was obtained with [Pd(PPh₃)₄]. The diene 1 also reacts with Fe(CO)₅ to form the complex [(C₇H₂F₆)Fe(CO)₄], and with [Rh(C₂H₄)₂(acac)] to give [(C₇H₂F₆)Rh(acac)] in which the diene acts as a bidentate ligand. Similar products could not be isolated from the reactions of 2 and 3. A stable adduct, believed to be [{C₇F₆(SnMe₃)₂}Rh(CO)₂(μ-Cl)₂Rh(CO)₂] has been isolated from the reaction between 2 and [Rh(CO)₂Cl]₂. This adduct reacts with PPh₃ to give the bridge-cleavage product [{C₇F₆(SnMe₃)₂}RhCl(CO)(PPh₃)₂]. Reaction of 1 with [Rh(CO)₂Cl]₂ gives an unstable adduct which could not be isolated, and 2 does not react at room temperature. The chloro derivative 3 reacts with [PdCl₂(PhCN)₂] to give the adduct [(C₇F₆Cl₂)PdCl(PhCN)], but 1 and 2 do not react under similar conditions. Stable substitution products [(C₇F₆R₂)M] (R = H, M = Fe(CO)₂(η-C₅H₅); R = SnMe₃, M = Fe(CO)₂(η-C₅H₅), Mn(CO)₅, Ir(CO)₂(PPh₃)₂, Rh(CO)₂(PPh₃)₂; R = Cl, M = Ir(CO)₂(PPh₃)₂, Rh(CO)₂(PPh₃)₂) have been isolated from the reactions of the dienes with carbonylmetal anions. Insertion of the CHCH bond occurs when 1 is heated with [MnMe(CO)₅] to give [{C₇F₆H₂C($\text{O)Me}M}$n(CO)₄], and this, on reaction with either PPh₃ or [Pt(PPh₃)₄], gives [(C₇F₆H₂COMe)Mn(CO)₄PPh₃].     

Corrigendum

Reactions of NaMn(CO)₃ with RuCl₂(PMe₃)₄, RuCl₂(dppm)₂ and RuCl₂(PPh₃)₃ lead either to an ionic species [Ru₂Cl₃(PMe₃)₆]+[Mn(CO)₅]^? or to metal—metal bonded RuMn compounds such as RuMn(μ-CO)₂(CO)₃(μ-dppm)₂ Cl, and, quite unexpectedly, to the μ-phosphido complex RuMn(μ-PPh₂)(CO)₆(PPh₃)₂ via a hydride intermediate.