Oxo-rhenium(V) complexes containing bis(diphenylphosphino)ethane and catecholate ligands

Bis(diphenylphosphino)ethane (dppe) complexes of the type ReOCl(dppe)(O-O), where O-O = catecholate or tetrachlorocatecholate dianion, were prepared by reacting ReOCl₃(dppe) with the catechol ligand in the presence of NEt₃. X-ray diffraction on the tetrachlorocatecholate compound showed that the molecule adopts a distorted octahedral structure, in which the dppe ligand and the bidentate catecholate lie in the equatorial plane, perpendicular to the ORe-Cl unit. In contrast, for ReOCl(PPh₃)₂(O-O), the position trans to the ReO bond is occupied by a catecholate oxygen, whereas the two PPh₃ ligands are trans to one another in the equatorial plane. The UV-Vis absorption spectrum of ReO(OMe)(dppe)(oxalate) is similar to those of ReO(OR)X₂(dppe) compounds, showing two weak bands for the spin-allowed d-d transitions from the filled interaxial d orbital in the xy plane into the inequivalent metal d_xz and d_yz orbitals, respectively. For the catecholate complexes, the spectra are dominated by charge-transfer transitions from the HOMO π orbital of the catecholate ligand into the d_xz and d_yz orbitals. Both the singlet-singlet and the singlet-triplet transitions are generally observed. No information could be obtained on the weaker d-d transitions for the catecholate compounds.     

Synthesis and coordination of the bifunctionalized ylides Ph2P(CH2)n(Ph)2PCHCOOMe (n = 1, 2) and ketenylidene Ph2P(CH2)2(Ph)2PCCO to Pd and Pt complexes

In this paper it is reported the synthesis of the phosphonium salts [Ph₂P(CH₂)_n(Ph)₂PCH₂COOMe]Br (n = 1 (1), 2 (2)) and [Ph₂P(CH₂COOMe)(CH₂)_n(Ph)₂PCH₂COOMe]Br₂ (n = 3 (3)) derived from the reactions of the diphosphines dppm, dppe and dppp with methyl bromoacetate. By reaction of the monophosphonium salt of dppm and dppe with the strong base Na[N(SiMe₃)₂] the corresponding carbonyl stabilized ylides Ph₂P(CH₂)_n(Ph)₂PCHCOOMe (n = 1 (4), 2 (5)) were obtained. The Ph₂P(CH₂)₂(Ph)₂PCHCOOMe (5) ylide was reacted with Pd(II) and Pt(II) substrates. From these reactions were isolated exclusively complexes in which the ylide was chelated to the metal through the free phosphine group and the ylidic carbon atom. A further reaction of the Ph₂P(CH₂)₂(Ph)₂PCHCOOMe (5) ylide with 1.5 equiv. of Na[N(SiMe₃)₂] gives the bifunctionalized ketenylidene Ph₂P(CH₂)₂(Ph)₂PCCO (6) system. This cumulenic ylide reacts with Pt(II) complexes to form a chelated derivative in which IR and NMR spectra suggest the breaking of the CC bond of the -CCO group.     

Alkoxy-substituted group 6 allenylidene complexes - Synthesis and properties

Bis(alkoxy)allenylidene complexes, [(CO)₅MCCC(OR′)OR], as well as mono(alkoxy)allenylidene complexes, [(CO)₅MCCC(OR′)Ph], of chromium and tungsten are accessible from propynones [HCCC(O)Ph] or propynoic acid esters [HCCC(O)OR; R = Et, (−)-menthyl, endo-bornyl] by the following reaction sequence: (a) deprotonation of the alkynes, (b) reaction with [(CO)₅M-THF] (M = Cr, W), and (c) alkylation of the resulting alkynyl metallate, [(CO)₅MCCC(O)R], with Meerwein salts. Vinylidene complexes, [(CO)₅MCC(R′)C(O)OR], are formed as a by-product by C_β-alkylation of the alkynyl metallate. Dimethylamine displaces one alkoxy substituent of the bis(alkoxy)allenylidene complexes to give dimethylamino(alkoxy)allenylidene complexes, [(CO)₅MCCC(OR)NMe₂]. The analogous reaction of dimethylamine with a mono(alkoxy)-substituted allenylidene complex affords the aminoallenylidene complex [(CO)₅CrCCC(NMe₂)Ph]. When the amine is used in large excess, the α,β-unsaturated aminocarbene complex [(CO)₅CrC(NMe₂)C(H)C(NMe₂)Ph] is additionally formed by addition of the amine across the C_αC_β-bond of the allenylidene ligand. The reaction of [(CO)₅MCCC(OEt)₂] with dimethyl ethylenediamine offers access to bis(amino)allenylidene complexes, in which C_γ is part of a five-membered heterocycle. Photolysis of bis(alkoxy)allenylidene complexes in the presence of triphenylphosphine yields tetracarbonyl- and tricarbonyl{bis(phosphine)}allenylidene complexes. Diethylaminopropyne inserts into the C_βC_γ bond of [(CO)₅MCCC(OEt)OMethyl] to give alkenylallenylidene complexes. Subsequent acid-catalyzed intramolecular cyclization affords a pyranylidene complex.     

Synthesis and structures of bimetallic silicon-containing imido alkylidene complexes of molybdenum Me2Si[CHMo(NAr)(ORF3)2]2 and PhVinSi[CHMo(NAr)(ORF3)2]2

Bimetallic alkylidene complexes of molybdenum (R_F3O)₂(ArN)MoCH-SiMe₂-CHMo(NAr)(OR_F3)₂ (1) and (R_F3O)₂(ArN)MoCH-SiPhVin-CHMo(NAr)(OR_F3)₂ (2) (Ar = 2,6-C₆H₃; R_F3 = CMe₂CF₃) have been prepared by the reactions of vinyl silicon reagents Me₂Si(CHCH₂)₂ and PhSi(CHCH₂)₃ with known alkylidene compound PhMe₂C-CHMo(NAr)(OR_F3)₂. Complexes 1 and 2 were structurally characterized. Ring opening metathesis polymerization (ROMP) of cyclooctene using compounds 1 and 2 as initiators led to the formation of high molecular weight polyoctenamers with predominant trans-units content in the case of 1 and predominant cis-units content in the case of 2.     

A new cumulene diiron complex related to the active site of Fe-only hydrogenases and its phosphine substituted derivatives: synthesis, electrochemistry and structural characterization

A new cumulene diiron complex related to the Fe-only hydrogenase active site [(μ-SCH₂C(S)CCH₂)Fe₂(CO)₆] (1) was obtained by treatment of (μ-LiS)₂Fe₂(CO)₆ with excess 1,4-dichloro-2-butyne. By controllable CO displacement of 1 with PPh₃ and bis(diphenylphosphino)methane (dppm), mono- and di-substituted complexes, namely [(μ-SCH₂C(S)CCH₂)Fe₂(CO)₅L] (2: L = PPh₃; 3: L = dppm) and [(μ-SCH₂C(S)CCH₂)Fe₂(CO)₄L₂] (4: L = PPh₃; 5: L = dppm) could be prepared in moderate yields. Treatment of 1 with bis(diphenylphosphino)ethane (dppe) afforded a double butterfly complex [(μ-SCH₂C(S)CCH₂)Fe₂(CO)₅]₂(μ-dppe) (7). With dppm in refluxing toluene, a dppm-bridged complex [(μ-SCH₂C(S)CCH₂)Fe₂(CO)₄(μ-dppm)] (6) was obtained. These model complexes were characterized by IR, ¹H, ³¹P NMR spectra and the molecular structures of 1, 2 and 5-7 were determined by single crystal X-ray analyses. The electrochemistry of 1-3 was studied and the electrocatalytic property of 1 was investigated for proton reduction in the presence of HOAc.     

Ruthenium hydride and vinyl complexes supported by nitrogen-oxygen mixed-donor ligands

The Schiff base, 2-chlorophenylsalicylaldimine (HL₁), is formed readily from salicylaldehyde and 2-chloroaniline. After deprotonation, this ligand is found to react as a bidentate mixed-donor chelate with the complexes [RuRCl(CO)(BTD)(PPh₃)₂] (R = H, CHCHC₆H₅, CHCHC₆H₄Me-4, CHCH^tBu, CCCPhCHPh; BTD = 2,1,3-benzothiadiazole) to form the compounds [RuR(L₁)(CO)(PPh₃)₂] through displacement of the chloride and BTD ligands. An analogous reaction occurs with the osmium complex [OsHCl(CO)(BTD)(PPh₃)₂] to provide [OsH(L₁)(CO)(PPh₃)₂]. The compound [Ru(CHCHC₆H₄Me-4)(L₂)(CO)(PPh₃)₂] is formed through reaction of salicylaldehyde (HL₂) with [Ru(CHCHC₆H₄Me-4)Cl(CO)(BTD)(PPh₃)₂] in the presence of base. Two further ligands were investigated to extend the study to encompass 5- and 4-membered chelates; 8-hydroxyquinoline (HL₃) and 2-hydroxy-4-methylquinoline (HL₄) react with [Ru(CHCHPh)Cl(CO)(BTD)(PPh₃)₂] and [Ru(CHCHC₆H₄Me-4)Cl(CO)(BTD)(PPh₃)₂] in the presence of base to yield the complexes [Ru(CHCHPh)(L₃)(CO)(PPh₃)₂] and [Ru(CHCHC₆H₄Me-4)(L₄)(CO)(PPh₃)₂], respectively. The crystal structure of [Ru(CHCHC₆H₄Me-4)(L₁)(CO)(PPh₃)₂] is reported.     

Addition of protic nucleophiles to alkynyl methoxy carbene ligands in diiron complexes

Different protic nucleophiles (i.e.Ph₂CNH, PhSH, MeCO₂H, PhOH) can be added to the CC bond of [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){C(OMe)CCTol}(Cp)₂][SO₃CF₃] (1), affording new diiron alkenyl methoxy carbene complexes.The additions of Ph₂CNH and MeCO₂H are regio and stereoselective, resulting in the formation of the 5-aza-1-metalla-1,3,5-hexatriene [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){C_α(OMe)C_βHC_γ(Tol)(NCPh₂)}(Cp)₂][SO₃CF₃] (2), and the 2-(acyloxy)alkenyl methoxy carbene complex [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){C_α(OMe)C_βHC_γ(Tol)OC(O)Me)}(Cp)₂][CF₃SO₃] (5); the E isomer of the former and the Z of the latter are formed exclusively.Conversely, the addition of PhSH is regio but not stereoselective; thus, both the E and Z isomers of [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){C_α(OMe)C_βHC_γ(Tol)(SPh)}(Cp)₂][SO₃CF₃] (3) are formed in comparable amounts.Compounds 3 and 5 are demethylated upon chromatography through Al₂O₃, resulting in the formation of the acyl complexes [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){C_α(O)C_βHC_γ(Tol)(SPh)}(Cp)₂] (4) and [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){C_α(O)C_βHC_γ(Tol)OC(O)Me}(Cp)₂] (6), respectively, both with a Z configured C_βC_γ bond.Finally, the reaction of 1 with PhOH proceeds only in the presence of an excess of Et₃N affording the 2-(alkoxy)alkenyl acyl complex [Fe₂{μ-CN(Me)(Xyl)}(μ- CO)(CO){C_α(O)C_βHC_γ(Tol)(OPh)}(Cp)₂] (7). The crystal structures of 4 · CH₂Cl₂ and 7 · 0.5CH₂Cl₂ have been determined by X-ray diffraction experiments.     

Non-aromatic stabilised form of 3,4-difluoropyrrole at triosmium clusters: N-H and C-H versus C-F activation

Reaction of 3,4-difluoropyrrole with the labile triosmium cluster [Os₃(CO)₁₀(CH₃CN)₂] affords products in which C-H, N-H and C-F bonds are cleaved under mild conditions. C-H and N-H bonds are cleaved to give [Os₃H(NCCFCFCH₂)(CO)₁₀] (1) a non-aromatic stabilised form of 3,4-difluoropyrrole. Thermolysis of 1 affords in moderate yields the compounds [Os₃H₂(CCCFCHNH)(CO)₉] (2) and [Os₃H₂(NCHCFCFC)(CO)₉] (3). For compound 3, C-H and N-H bonds are cleaved with concomitant migration of H atoms to the metal framework. In contrast, for compound 2 activation of C-H and C-F bonds leads to coordination of the ligand through the carbon atoms, acting as a four-electron donating species.     

Regioselective addition of bifunctional oximehydroxamic acid by the hydroxamic group to Pt(IV)-coordinated nitriles

The metal-mediated coupling between the nitriles RCN in the platinum(IV) complexes trans-[PtCl₄(RCN)₂] (RMe, Et, CH₂Ph, Ph), cis/trans-[PtCl₄(MeCN)(Me₂SO)] and the newly synthesized bifunctional oximehydroxamic acid, viz. N,2-dihydroxy-5-(1-hydroxyiminoethyl)benzamide, proceeds smoothly in CH₂Cl₂ at 40-45 °C to accomplish the new metallaligands HNC(R)ONHC(O)C₆H₃(2-OH)(5-C(Me)NOH) with pendant oxime functionalities due to the regioselective addition of the reagent via its hydroxamic groups. The obtained iminoligands exist in hydroxamic/hydroximic tautomeric equilibrium in solution. The structures of the isolated compounds are based on elemental analyses (C, H, N), IR, 1D ¹H, ¹³C{¹H}, and 2D NMR correlation experiments, i.e. ¹H,¹³C-COSY, ¹H,¹³C long range COSY, ¹H,¹⁵N-COSY, and ¹H,¹⁵N long range COSY.     

Palladium(II) amido complexes with an unsymmetrical PNP′ pincer-type coordination and a new (E,E)-tetradentate diphosphinoazine coordination mode

Cationic palladium(II) complexes [PdCl{PR₂CH₂C(Bu^t)NNC(Bu^t)CH₂PR₂}]Cl, where R = isopropyl, cyclohexyl or tert-butyl, were synthesized by the reactions of the corresponding diphosphinoazines with bis(acetonitrile)palladium(II) dichloride. When bis(benzonitrile)palladium(II) dichloride was used instead, in the molar ratio of 2:1 to the diphosphinoazine, a new complex was isolated with the isopropyl ligand showing a previously unknown (E,E) tetradentate coordination mode. Crystal and molecular structure was determined by X-ray diffraction. The solid complex was a racemate of two axially chiral enantiomers and the chirality was preserved in solution. Reactions of the cationic complexes with triethylamine gave complexes [PdCl{PR₂CHC(Bu^t)NNC(Bu^t)CH₂PR₂}], containing deprotonated diphosphinoazines in ene-hydrazone unsymmetrical pincer-like configuration. The complexes represent several of the still rare examples of Pd(II) amido bis(phosphine) complexes with a chlorine atom covalently bonded trans to the amide nitrogen.     

Synthesis and characterisation of isomeric cycloaurated complexes derived from the iminophosphorane Ph3PNC(O)Ph

Using different organomercury substrates, two isomeric cycloaurated complexes derived from the stabilised iminophosphorane Ph₃PNC(O)Ph were prepared. Reaction of Ph₃PNC(O)Ph with PhCH₂Mn(CO)₅ gave the manganated precursor (CO)₄Mn(2-C₆H₄C(O)NPPh₃), metallated on the C(O)Ph substituent, which yielded the organomercury complex ClHg(2-C₆H₄C(O)NPPh₃) by reaction with HgCl₂ in methanol. Transmetallation of the mercurated derivative with Me₄N[AuCl₄] gave the cycloaurated iminophosphorane AuCl₂(2-C₆H₄C(O)NPPh₃) with an exo PPh₃ substituent. The endo isomer AuCl₂(2-C₆H₄Ph₂PNC(O)Ph) [aurated on a PPh₃ ring] was obtained by an independent reaction sequence, involving reaction of the diarylmercury precursor Hg(2-C₆H₄P(NC(O)Ph)Ph₂)₂ [prepared from the known compound Hg(2-C₆H₄PPh₂)₂ and PhC(O)N₃] with Me₄N[AuCl₄]. Both of the isomeric iminophosphorane derivatives were structurally characterised, together with the precursors (2-HgClC₆H₄)C(O)NPPh₃ and (CO)₄Mn(2-C₆H₄C(O)NPPh₃). The utility of ³¹P NMR spectroscopy in monitoring reaction chemistry in this system is described.     

Diphosphinoazine rhodium(III) and iridium(III) octahedral complexes

Rhodium(III) and iridium(III) octahedral complexes of general formula [MCl₃{R₂PCH₂C(Bu^t)NNC(Bu^t)CH₂PR₂}] (M = Rh, Ir; R = Ph, c-C₆H₁₁, Prⁱ, Bu^t; not all the combinations) were prepared either from the corresponding diphosphinoazines and RhCl₃ · 3H₂O or by the oxidation of previously reported bridging complexes [{MCl(1,2-η:5,6-η-CHCHCH₂CH₂CHCHCH₂CH₂)}₂{μ-R₂PCH₂C(Bu^t)NNC(Bu^t)CH₂PR₂}] with chlorine-containing solvents. Depending on the steric properties of the ligands, complexes with facial or meridional configuration were obtained. Crystal and molecular structures of three facial and two meridional complexes were determined by X-ray diffraction. Hemilability of ligand in the complex fac-[RhCl₃{(C₆H₁₁)₂PCH₂C(Bu^t)NNC(Bu^t)CH₂P(C₆H₁₁)₂}] consisting in reversible decoordination of the phosphine donor group in the six-membered ring was observed as the first step of isomerization between fac and mer isomers.     

Iridium(III)-vinylidene chemistry: Conversion of an iridacyclopentadiene-chlorido complex and terminal alkynes to iridacyclopentadiene-vinyl complexes

The reactions of [κ²(C¹,C⁴)-CRCRCRCR](PPh₃)₂Ir(Cl) (9, R = CO₂Me) with propargyl alcohol derivatives (2-propyn-1-ol, 2-methyl-3-butyn-2-ol, 1-ethynylcyclopentanol, and 1-ethynylcyclooctanol), in the presence of water leads to the formation of iridium(III)-vinyl complexes bearing the general structure [κ²(C¹,C⁴)-CRCRCRCR](PPh₃)₂Ir(CO)(κ¹-vinyl) where vinyl = -CHCH₂, -(E)-CHCHMe, -CHC(CH₂)₄, or -CHC(CH₂)₇. In these, the CO ligand was derived from the terminal carbon of the starting alkyne and the oxygen atom from water. Under anhydrous conditions, 9 undergoes reaction with 2-propyn-1-ol to give trimethyl 1,3-dihydro-3-oxo-4,5,6-isobenzofurantricarboxylate, the result of a cycloaromatization/transesterification involving the buta-1,3-dien-1,4-diyl ligand in 9 and 2-propyn-1-ol.     

Ferrocenyl-substituted allenylidene complexes of chromium, molybdenum and tungsten: Synthesis, structure and reactivity

Bis(ferrocenyl)-substituted allenylidene complexes, [(CO)₅MCCCFc₂] (1a-c, Fc = (C₅H₄)Fe(C₅H₅), M = Cr (a), Mo (b), W (c)) were obtained by sequential reaction of Fc₂CO with Me₃Si-CCH, KF/MeOH, n-BuLi, and [(CO)₅M(THF)]. For the synthesis of related mono(ferrocenyl)allenylidene chromium complexes, [(CO)₅CrCCC(Fc)R] (R = Ph, NMe₂), three different routes were developed: (a) reaction of the deprotonated propargylic alcohol HCCC(Fc)(Ph)OH with [(CO)₅Cr(THF)] followed by desoxygenation with Cl₂CO, (b) Lewis acid induced alcohol elimination from alkenyl(alkoxy)carbene complexes, [(CO)₅CrC(OR)CHC(NMe₂)Fc], and (c) replacement of OMe in [(CO)₅CrCCC(OMe)NMe₂] by Fc. Complex 1a was also formed when the mono(ferrocenyl)allenylidene complex [(CO)₅CrCCC(Fc)NMe₂] was treated first with Li[Fc] and the resulting adduct then with SiO₂. The replacement route (c) was also applied to the synthesis of an allenylidene complex (7a) with a CC spacer in between the ferrocenyl unit and C_γ of the allenylidene ligand, [(CO)₅CrCCC(NMe₂)-CCFc]. The related complex containing a CHCH spacer (9a) was prepared by condensation of [(CO)₅CrCCC(Me)NMe₂] with formylferrocene in the presence of NEt₃. The bis(ferrocenyl)-substituted allenylidene complexes 1a-c added HNMe₂ across the C_α-C_β bond to give alkenyl(dimethylamino)carbene complexes and reacted with diethylaminopropyne by regioselective insertion of the CC bond into the C_β-C_γ bond to afford alkenyl(diethylamino)allenylidene complexes, [(CO)₅MCCC(NEt₂)CMeCFc₂]. The structures of 5a, 7a, and 9a were established by X-ray diffraction studies.     

Reactivity of alkynyl Pd(II) azido complexes toward organic isocyanides, isothiocyanates, and nitriles

Alkynyl Pd(II) azido complexes of the type [Pd(N₃)(CCR)L₂] (1-3) were obtained by reactions of aqueous NaN₃ with [Pd(Cl)(CCR)L₂] (R = Ph or C(O)OMe). Treating compounds 1-3 with organic isocyanides (R-NC) afforded novel complexes, trans-[Pd(CCPh)(NCNR)(PMe₃)₂] (R = 2,6-Me₂C₆H₃ (4) or 2,6-Et₂C₆H₃ (5)) and trans-[Pd(CCR)(CN₄-t-Bu)L₂] (6: L = PMe₃, R = Ph; 7: L = PEt₃, R = C(O)OMe; 8: L = PMe₃, R = C(O)OMe), which contain either a carbodiimido or a C-coordinated tetrazolato group. Reactions of compounds 1 and 2 with R-NCS (R = 2,6-Me₂C₆H₃ or CH₂CH₃) and 1,4-phenylene diisothiocyanate (C₆H₄(NCS)₂) smoothly proceeded to give tetrazole-thiolato complexes, trans-[Pd(CCPh)(SCN₄-R)L₂] (L = PMe₃, R = Et (9) or 2,6-Me₂C₆H₃ (10); L = PEt₃, R = 2,6-Me₂C₆H₃ (11)), and a phenylene-bridged dinuclear Pd(II) tetrazole-thiolato complex, [(PEt₃)₂(CCPh)Pd(SCN₄-(μ-C₆H₄)-SCN₄)Pd(CCPh)(PEt₃)₂] (12), respectively. Complexes 9-12 contain the Pd-S bond that is formed by the dipolar cycloaddition of the organic isothiocyanate to the Pd-azido bond. In contrast, the corresponding reactions of compounds 1and 2 with C₆F₅CN and Me₃SiCN (organic nitriles, R-CN) gave an N-coordinated Pd(II)-tetrazolato compound {trans-[Pd(CCPh)(N₄C-C₆F₅)(PMe₃)₂] (13)} and a mixture of Pd(II)-cyano complexes {trans-[Pd(CCPh)(CN)(PEt₃)₂] (14) and [Pd(CN)₂(PEt₃)₂] (15)}, respectively. Bis(phosphine) bis(cyano) complexes of Pd and Ni, [M(CN)₂L₂] (L = PEt₃, PMe₃; L₂ = DEPE), could be obtained independently by the reactions of [M(N₃)₂L₂] with excess Me₃SiCN in organic solvents.     

Synthesis and reactivity of gold(III) complexes containing cycloaurated iminophosphorane ligands

Transmetallation reactions of ortho-mercurated iminophosphoranes (2-ClHgC₆H₄)Ph₂PNR with [AuCl₄]⁻ gives new cycloaurated iminophosphorane complexes of gold(III) (2-Cl₂AuC₆H₄)Ph₂PNR [R = (R,S)- or (S)-CHMePh, p-C₆H₄F, ^tBu], characterised by NMR and IR spectroscopies, ESI mass spectrometry and an X-ray structure determination on the chiral derivative R = (S)-CHMePh. The chloride ligands of these complexes can be readily replaced by the chelating ligands thiosalicylate and catecholate; the resulting derivatives show markedly higher anti-tumour activity versus P388 murine leukaemia cells compared to the parent chloride complexes. Reaction of (2-Cl₂AuC₆H₄)Ph₂PNPh with PPh₃ results in displacement of a chloride ligand giving the cationic complex [(2-Cl(PPh₃)AuC₆H₄)Ph₂PNPh]⁺, indicating that the PN donor is strongly bonded to the gold centre.     

Synthesis and solid-state structures of (triphos)iridacyclopentadiene complexes as models for vinylidene intermediates in the [2 + 2 + 1] cyclotrimerization of alkynes

The iridium 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos) complexes [{κ²(C¹,C⁴)-CRCRCRCR}{CH₃C(CH₂PPh₂)₃}Ir(NCMe)]BF₄ (2-NCMe, R = CO₂Me) and [{κ²(C¹,C⁴)-CRCRCRCR}{CH₃C(CH₂PPh₂)₃}Ir(CO)]BF₄ (2-CO, R = CO₂Me) serve as models for proposed iridium-vinylidene intermediates of relevance to the [2 + 2 + 1] cyclotrimerization of alkynes. The solid-state structures of 2-NCMe, 2-CO, and [κ²(C¹,C⁴)-CRCRCRCR]{CH₃C(CH₂PPh₂)₃}Ir(Cl) (2-Cl), were determined by X-ray crystallography.     

Ketimine synthesis in the coordination sphere of thallium (I)

[AuTl(C₆F₅)₂(en)] (en = ethylenediamine) reacts with cyclic ketones as cyclopentanone (Cy⁵O), cyclohexanone (Cy⁶O) or cycloheptanone (Cy⁷O) in 1:1 or 1:2 molar ratio leading to products of stoichiometry [AuTl(C₆F₅)₂{Cy^xN(CH₂)₂NH₂}] (x = 5 1, 6 2 or 7 3), or [AuTl(C₆F₅)₂{Cy^xN(CH₂)₂NCy^x}] (x = 5 4, 6 5 or 7 6). Addition of ethylenediamine to the ketimine complexes in chloroform regenerates [AuTl(C₆F₅)₂(en)], the starting material, and the free ketimines, as their NMR and mass spectra evidenced. The ketimine complexes display luminescence in solid state at room temperature and at 77 K at higher wavelengths than the diamine starting product (505 nm). The excited states responsible for this behaviour are assigned to orbitals due to the gold-thallium interactions.     

Synthesis and reactivity of five- and six-coordinate hydrido(vinyl) iridium(III) complexes

The reaction of the dihydrido iridium(III) precursor [IrH₂(Cl)(PiPr₃)₂] (5) with internal alkynes RCC(CO₂Me) (R = Me, CO₂Me) afforded the five-coordinate hydrido(vinyl) complexes [IrH(Cl){(E)-C(R)CH(CO₂Me)}(PiPr₃)₂] (6, 7), via insertion of the alkyne into one of the IrH bonds. Compounds 6 and 7 are also accessible by careful hydrogenation of the alkyne iridium(I) derivatives trans-[IrCl{RCC(CO₂Me)}(PiPr₃)₂] (9, 10), the latter being prepared from in situ generated trans-[IrCl(C₈H₁₄)(PiPr₃)₂] and RCC(CO₂Me). UV irradiation of 6 (R = CO₂Me) led to the formation of the isomer [IrH(Cl){κ²(C,O)-C(CO₂Me)CHC(OMe)O}(PiPr₃)₂] (3) having the vinyl ligand coordinated in a bidentate fashion. While 6 reacted with acetonitrile and CO to afford the six-coordinate iridium(III) compounds [IrH(Cl){(E)-C(CO₂Me)CH(CO₂Me)}(L′)(PiPr₃)₂] (11, 12), treatment of 6 with LiC₅H₅ gave the half-sandwich-type complex [(η⁵-C₅H₅)IrH{(E)-C(CO₂Me)CH(CO₂Me)}(PiPr₃)] (13) by, the loss of one PiPr₃. The reaction of 3 with CO under pressure resulted in the formation of [IrH(Cl){(Z)-C(CO₂Me)CH(CO₂Me)}(CO)(PiPr₃)₂] (14) in which, in contrast to the stereoisomer 12, the two CO₂Me substituents are trans disposed.     

Gas-phase molecular structures of substituted 1,3-bisketenes: A challenge for theory and experiment

Molecular structures of dimethylbis(trimethylsilylketyl)silane (Me₂Si[C(SiMe₃)CO]₂), dimethylbis(trimethylgermylketyl)silane (Me₂Si[C(GeMe₃)CO]₂), and dimethylbis(trimethylstannylketyl)germane (Me₂Ge[C(SnMe₃)CO]₂) have been studied in the gas phase by electron diffraction accompanied by high level ab initio and DFT calculations. Extensive theoretical conformational analyses of the molecules in the vapour predicted a possibility of existence of two types of conformers with small energy differences. The first type had gauche-gauche arrangements of the ketenyl groups in the central C(CO)XC(CO) fragments directed away from each other. The second type had nearly syn-gauche arrangements of the ketenyl groups. In addition, the energy differences were found to depend on the level of computations used. The experimental analysis, in turn, was unable to distinguish between different conformers due to the large number of similar overlapping distances. The experimental data were fitted by an averaged single-conformer model, which nevertheless allowed reliable determination of bonds and bonded angles in the molecules. Main experimental (r_h1) structural parameters for Me₂Si[C(SiMe₃)CO]₂, Me₂Si[C(GeMe₃)CO]₂, and Me₂Ge[C(SnMe₃)CO]₂, i.e. Me₂X[C(YMe₃)CO]₂ (X,Y = Si, Ge, Sn), are (X-C)_mean 187.7(1) pm, 194.6(2) pm, 216.1(3) pm; (Y-C)_mean, 187.7(1) pm, 188.8(8) pm, 194.6(4) pm; (CC)_mean, 135.3(5) pm, 131.6(5) pm, 131.5(13) pm; (CO)_mean, 117.0(7) pm, 117.4(7) pm, 119.0(11) pm; (C-H)_mean, 110.6(7) pm, 110.0(4) pm, 109.1(13) pm; (X(Y)-CC)_mean, 114.4(2)°, 115.6(1)°, 115.6(2)°; (C-X(Y)-C_Me)_mean, 108.3(3)°, 108.4(3)°, 108.9(13)°; C(2)-C(1)-Y(4)-C(10), −19(6)°, 5(4)°, −9(10)°; C(7)-C(6)-Y(9)-C(38),−22(7)°, −32(3)°, −9(10)°; C(2)-C(1)-X(5)-C(6), 128(4)°, 142(1)°, 108(9)°; C(7)-C(6)-X(5)-C(1), 92(6)°, 115(2)°, 108(9)°, respectively.