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1.
Dalton Trans ; 53(5): 1942-1946, 2024 Jan 30.
Article in English | MEDLINE | ID: mdl-38205632

ABSTRACT

The marine natural product norzooanemonin (1,3-dimethylimidazolium-4-carboxylate) has been used to prepare a series of carboxyl- or carboxylate-functionalized N-heterocyclic carbene (NHC) gold(I) complexes from [(Me2S)AuCl] in the presence of potassium carbonate. The potential of the resulting mono- and dicarbene complexes to act as cytotoxic or antibacterial drugs was investigated.

2.
Chemistry ; 28(4): e202104139, 2022 Jan 19.
Article in English | MEDLINE | ID: mdl-34878696

ABSTRACT

The lithium salts of anionic N-heterocyclic thiones and selones [{(WCA-IDipp)E}Li(toluene)] (1: E=S; 2: E=Se; WCA=B(C6 F5 )3 , IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene), which contain a weakly coordinating anionic (WCA) borate moiety in the imidazole backbone were reacted with Me3 SiCl, to furnish the silylated adducts (WCA-IDipp)ESiMe3 (3: E=S; 4: E=Se). The reaction of the latter with [(η5 -C5 Me5 )MCl2 ]2 (M=Rh, Ir) afforded the rhodium(III) and iridium(III) half-sandwich complexes [{(WCA-IDipp)E}MCl(η5 -C5 Me5 )] (5-8). The direct reaction of the lithium salts 1 and 2 with a half or a full equivalent of [M(COD)Cl]2 (M=Rh, Ir) afforded the monometallic complexes [{(WCA-IDipp)E}M(COD)] (9-12) or the bimetallic complexes [µ2 -{(WCA-IDipp)E}M2 (COD)2 (µ2 -Cl)] (13-16), respectively. The bonding situation in these complexes has been investigated by means of density functional theory (DFT) calculations, revealing thiolate or selenolate ligand character with negligible metal-chalcogen π-interaction.

3.
Inorg Chem ; 60(12): 9019-9028, 2021 Jun 21.
Article in English | MEDLINE | ID: mdl-34042436

ABSTRACT

Anionic N-heterocyclic carbenes with weakly coordinating borate, aluminate, and gallate moieties of the type [(F5C6)3E-NHC]- (E = B, Al, Ga) were isolated as lithium salts by the lithiation of 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (IMes) or 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene (IDipp) followed by the addition of E(C6F5)3 (E = B, Al, Ga). Treatment with elemental selenium afforded the lithium salts of the corresponding anionic selenourea derivatives [{(F5C6)3E-NHC}Se]- (NHC = IMes, E = B; NHC = IDipp, E = B, Al, Ga), which were examined, among other things, by means of 77Se{1H} NMR spectroscopy to assess the π-accepting properties of the WCA-NHC ligands in comparison with their neutral NHC congeners.

4.
Chemistry ; 27(13): 4349-4363, 2021 Mar 01.
Article in English | MEDLINE | ID: mdl-33094865

ABSTRACT

The lithium complexes [(WCA-NHC)Li(toluene)] of anionic N-heterocyclic carbenes with a weakly coordinating anionic borate moiety (WCA-NHC) reacted with iodine, bromine, or CCl4 to afford the zwitterionic 2-halogenoimidazolium borates (WCA-NHC)X (X=I, Br, Cl; WCA=B(C6 F5 )3 , B{3,5-C6 H3 (CF3 )2 }3 ; NHC=IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, or NHC=IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene). The iodine derivative (WCA-IDipp)I (WCA=B(C6 F5 )3 ) formed several complexes of the type (WCA-IDipp)I⋅L (L=C6 H5 Cl, C6 H5 Me, CH3 CN, THF, ONMe3 ), revealing its ability to act as an efficient halogen bond donor, which was also exploited for the preparation of hypervalent bis(carbene)iodine(I) complexes of the type [(WCA-IDipp)I(NHC)] and [PPh4 ][(WCA-IDipp)I(WCA-NHC)] (NHC=IDipp, IMes). The corresponding bromine complex [PPh4 ][(WCA-IDipp)2 Br] was isolated as a rare example of a hypervalent (10-Br-2) system. DFT calculations reveal that London dispersion contributes significantly to the stability of the bis(carbene)halogen(I) complexes, and the bonding was further analyzed by quantum theory of atoms in molecules (QTAIM) analysis.

5.
Dalton Trans ; 49(38): 13207-13217, 2020 Oct 06.
Article in English | MEDLINE | ID: mdl-32785308

ABSTRACT

Several group 16 adducts of the type [(WCA-IDipp)E]Li(solv.) that bear an anionic N-heterocyclic carbene ligand with a weakly coordinating borate moiety (WCA-IDipp, WCA = B(C6F5)3, IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, E = O, S, Se, Te) were prepared. This was achieved by deprotonation of the corresponding ketone (IDipp)O or thione (IDipp)S with n-BuLi and subsequent reaction with B(C6F5)3 or by direct reaction of [WCA-IDipp]Li(toluene) with elemental Se or Te. The oxygen, sulfur and selenium adducts can be protonated to give derivatives (WCA-IDipp)EH (E = O, S, Se), whereas the oxidation of the sulfur and selenium adducts yielded neutral disulfide and diselenide species (WCA-IDipp)2E2 (E = S, Se).

6.
Chemistry ; 26(65): 14878-14887, 2020 Nov 20.
Article in English | MEDLINE | ID: mdl-32721063

ABSTRACT

Chloride abstraction from the complexes [(η6 -p-cymene){(IDipp)P}MCl] (2 a, M=Ru; 2 b, M=Os) and [(η5 -C5 Me5 ){(IDipp)P}IrCl] (3 b, IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF ) in the presence of trimethylphosphine (PMe3 ), 1,3,4,5-tetramethylimidazolin-2-ylidene (Me IMe) or carbon monoxide (CO) afforded the complexes [(η6 -p-cymene){(IDipp)P}M(PMe3 )]BArF ] (4 a, M=Ru; 4 b, M=Os), [(η6 -p-cymene){(IDipp)P}Os(Me IMe)]BArF ] (5) and [(η5 -C5 Me5 ){(IDipp)P}IrL][BArF ] (6, L=PMe3 ; 7, L=Me IMe; 8, L=CO). These cationic N-heterocyclic carbene-phosphinidene complexes feature very similar structural and spectroscopic properties as prototypic nucleophilic arylphosphinidene complexes such as low-field 31 P NMR resonances and short metal-phosphorus double bonds. Density functional theory (DFT) calculations reveal that the metal-phosphorus bond can be described in terms of an interaction between a triplet [(IDipp)P]+ cation and a triplet metal complex fragment ligand with highly covalent σ- and π-contributions. Crystals of the C-H activated complex 9 were isolated from solutions containing the PMe3 complex, and its formation can be rationalized by PMe3 dissociation and formation of a putative 16-electron intermediate [(η5 -C5 Me5 )Ir{P(IDipp)}I][BArF ], which undergoes C-H activation at one of the Dipp isopropyl groups and addition along the iridium-phosphorus bond to afford an unusual η3 -benzyl coordination mode.

7.
Chemistry ; 25(70): 16148-16155, 2019 Dec 13.
Article in English | MEDLINE | ID: mdl-31625641

ABSTRACT

The reaction of 1,2-dipiperidinoacetylene (1) with 0.5 equivalents of SnCl2 or GeCl2 ⋅dioxane afforded the 1,2,3,4-tetrapiperidino-1,3-cyclobutadiene tin and germanium dichloride complexes 2 a and 2 b, respectively. A competing redox reaction was observed with excess amounts of SnCl2 , which produced a tetrapiperidinocyclobutadiene dication with two trichlorostannate(II) counterions. Heating neat 1 to 110 °C for 16 h cleanly produced the dimer 1,3,4,4-tetrapiperidino-3-buten-1-yne (3); its reaction with stoichiometric amounts of SnCl2 or GeCl2 ⋅dioxane furnished the 1,3,4,4-tetrapiperidino-1,2-cyclobutadiene tin and germanium dichloride complexes 4 a and 4 b, respectively. Transition-metal complexes containing this novel four-membered cyclic bent allene (CBA) ligand were prepared by reaction of 3 with [(tht)AuCl], [RhCl(CO)2 ]2 , and [(Me3 N)W(CO)5 ] to form [(CBA)AuCl] (5), [(CBA)RhCl(CO)2 ] (6), and [(CBA)W(CO)5 ] (7). The molecular structures of all compounds 2-7 were determined by X-ray diffraction analyses, and density functional theory (DFT) calculations were carried out to rationalise the formation of 3 and 4 a.

8.
Dalton Trans ; 48(35): 13430-13439, 2019 Sep 21.
Article in English | MEDLINE | ID: mdl-31441475

ABSTRACT

Diphosphine chelate ligands are essential in many catalytic processes with both the electronic structure and bite angle having a dramatic influence on the coordination behavior and catalytic performance. The synthesis of a new class of diferrocenylmercury-supported diphosphine chelate ligands was accomplished by the reaction of (ortho-diphenylphosphino)ferrocenyl sulfinate (2) with t-BuLi, followed by treatment with mercury(ii) chloride. Two diastereomers, 4a (pSpR-, meso-isomer) and 4b (pSpS-isomer), differ in the orientation of the ferrocene moiety relative to the central Ph2PC5H3-Hg-C5H3PPh2 bridging entity. They were isolated independently and fully characterized in solution and in the solid state by single crystal X-ray diffraction analysis. Key characteristics of these ligands are their exceptionally wide and flexible bite angles and the unique stereochemical environment that is achieved upon coordination to transition metals. Complexation to Pd(ii)Cl2 gives rise to unusual square-planar trans-chelate complexes 5a (meso) and 5b (pSpS). In competition reactions, 4a and 4b show similar reactivity toward Pd(ii)Cl2. The molecular structures of 5a and 5b exhibit short PdHg contacts, possibly indicating secondary metallophilic interactions as further evidenced by bond-critical points between Pd and Hg that were identified by AIM analyses.

9.
Chem Commun (Camb) ; 55(72): 10709-10712, 2019 Sep 16.
Article in English | MEDLINE | ID: mdl-31429453

ABSTRACT

The reaction of the phosphorus and arsenic dihalides (WCA-IDipp)ECl2 (E = P, As) that bear an anionic N-heterocyclic carbene ligand with a weakly coordinating borate moiety (WCA = B(C6F5)3, IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with (IDipp)PSiMe3 afforded the monochlorides (WCA-IDipp)E(Cl)P(IDipp), which can be transformed into the cationic dipnictenes [(WCA-IDipp)EP(IDipp)][GaCl4] or neutral radicals [(WCA-IDipp)EP(IDipp)] by treatment with GaCl3 or reduction with 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine.

10.
Chemistry ; 25(57): 13119-13123, 2019 Oct 11.
Article in English | MEDLINE | ID: mdl-31433085

ABSTRACT

Arsenic monophosphide (AsP) species supported by two different N-heterocyclic carbenes were prepared by reaction of (IDipp)PSiMe3 (1) (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with (IMes)AsCl3 (2) (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) to afford the dichloride [(IMes)As(Cl)P(IDipp)]Cl (3), which upon reduction with KC8 furnished heteroleptic [(IMes)AsP(IDipp)] (4). The corresponding mono- and dications [(IMes)AsP(IDipp)][PF6 ], [5]PF6 , and [(IMes)AsP(IDipp)][GaCl4 ]2, [6][GaCl4 ]2 , respectively, were prepared by one-electron oxidation of 4 with ferrocenium hexafluorophosphate, [Fc]PF6, or by chloride abstraction from 3 with two equivalents of GaCl3 , respectively. Compounds 4-6 represent rare examples of heterodiatiomic interpnictogen compounds, and X-ray crystal structure determinations together with density functional theory (DFT) calculations reveal a consecutive shortening of the As-P bond lengths and increasing bond order, in agreement with the presence of an arsenic-phosphorus single bond in 4 and a double bond in 62+ . The EPR signal of the cationic radical [5]+. indicates a symmetric spin distribution on the AsP moiety through strong hyperfine coupling with the 75 As and 31 P nuclei.

11.
Chemistry ; 25(26): 6517-6522, 2019 May 07.
Article in English | MEDLINE | ID: mdl-30932249

ABSTRACT

For the first time, a catalytic protocol for a highly selective hydrogen isotope exchange (HIE) of phenylacetic acid esters and amides under very mild reaction conditions is reported. Using a homogeneous iridium catalyst supported by a bidentate phosphine-imidazolin-2-imine P,N ligand, the HIE reaction on a series of phenylacetic acid derivatives proceeds with high yields, high selectivity, and with deuterium incorporation up to 99 %. The method is fully adaptable to the specific requirements of tritium chemistry, and its effectiveness was demonstrated by direct tritium labeling of the fungicide benalaxyl and the drug camylofine. Further insights into the mechanism of the HIE reaction with catalyst 1 have been provided utilizing DFT calculations, NMR studies, and X-ray diffraction analysis.

12.
Dalton Trans ; 48(13): 4228-4238, 2019 Mar 26.
Article in English | MEDLINE | ID: mdl-30843910

ABSTRACT

The half-sandwich 1,3-bis(trimethylsilyl)allyl and bis(trimethylsilyl)amido ruthenium complexes [(η5-C5Me5)RuX] (X = η3-C3H3(SiMe3)2, 1; X = N(SiMe3)2, 2) were prepared by reaction of tetranuclear [(η5-C5Me5)RuCl]4 with four equivalents of K[C3H3(SiMe3)2] or Na[N(SiMe3)2]. Complexes 1 and 2 are formally 16- and 14-electron complexes, respectively, and exhibit γ-agostic C-HRu interactions in the solid state, which were further investigated by density functional theory (DFT) calculations and quantum theory of atoms in molecules (QTAIM) analysis. The acid-base reaction of the amido complex 2 with 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (ImDippNH) afforded the imidazolin-2-iminato complex [(η5-C5Me5)Ru(NImDipp)] (4); 4 was also obtained from the reaction of [(η5-C5Me5)RuCl]4 with the lithium reagent [(ImDippN)Li]2. 4 represents the first terminal imidazolin-2-iminato complex with a late transition metal and shows a rare one-legged piano stool ("pogo stick") geometry with a short Ru-N bond of 1.8607(15) Å. The reaction of 4 with tert-butyl isocyanate (tBuNCO) gave the ureato complex [(η5-C5Me5)Ru{ImDippN(C[double bond, length as m-dash]O)NtBu}] (5) by [2 + 2] cycloaddition. This reactivity together with a DFT study on the bonding situation in 4 suggest a close similarity with related half-sandwich imido complexes [(arene)M(NR)] (M = Ru, Os) and [CpM(NR)] (M = Rh, Ir).

13.
Angew Chem Int Ed Engl ; 57(22): 6552-6557, 2018 05 28.
Article in English | MEDLINE | ID: mdl-29633536

ABSTRACT

A diphosphine chelate ligand with a wide and flexible bite angle, a unique stereochemical environment, and redox-active and ambiphilic character is reported. Initially generated as its HgCl2 complex by reaction of 1,2-fc(PPh2 )(SnMe3 ) (fc=ferrocenediyl) with HgCl2 in acetone, treatment with [n-Bu4 N]CN readily liberates the free chiral bidentate ligand. An intermolecular ClHg-Cl→Hgfc2 (2.9929(13) Å) interaction that is unprecedented in ambiphilic ligand chemistry is seen in the solid structure of Hg(fcPPh2 )2 ⋅HgCl2 where the bridging mercury atom acts as a σ-acceptor. Furthermore, a bis-[Rh(COD)Cl] complex is introduced, which displays relatively short Rh⋅⋅⋅Hg contacts of 3.4765(5) and 3.4013(1) Å. Wiberg indices of 0.12 are determined for these Rh⋅⋅⋅Hg interactions and an AIM analysis reveals bond paths with an electron density ρ(r) of 1.2×10-2 and 1.4×10-2  e/a03 at the bond critical points.

14.
Dalton Trans ; 46(45): 15859-15864, 2017 Nov 21.
Article in English | MEDLINE | ID: mdl-29114655

ABSTRACT

Heteroleptic N-heterocyclic dicarbene-diphosphorus species were prepared by reaction of the carbene-phosphinidene adduct (IPr)PSiMe3 (1, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with the carbene-phosphorus trichloride adduct (IMes)PCl3 (2, IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene), which furnished the dichloride [(IPr)PPCl(IMes)]Cl (3). Reduction of 3 with potassium graphite (KC8) afforded [(IPr)PP(IMes)] (4). The corresponding radical cation [(IPr)PP(IMes)]˙+ (5˙+) is isolated as [5]PF6 by reaction of 4 with ferrocenium hexafluorophosphate, whereas complexes containing the corresponding dication [(IPr)PP(IMes)]2+ (62+) can be isolated as the gallate and borate salts [6](GaCl4)2 and [6](BArF)2 by chloride abstraction from 3 with GaCl3 or sodium tetrakis[bis(3,5-trifluoromethyl)phenyl]borate (NaBArF), respectively. The asymmetric set of N-heterocyclic carbene ligands allows to establish 1JPP coupling constants of 249 Hz for 4 and 543 Hz for [6](GaCl4)2. Based on X-ray diffraction analyses, the molecular structures of 4, 5˙+ and 62+ reveal a consecutive shortening of the P-P bond lengths, in agreement with the presence of a phosphorus-phosphorus single bond in 4 and a double bond in 62+, which is best described as a dicationic diphosphene according to density functional theory (DFT) calculations.

15.
Inorg Chem ; 56(17): 10785-10793, 2017 Sep 05.
Article in English | MEDLINE | ID: mdl-28829597

ABSTRACT

Half-sandwich complexes of the N-heterocyclic carbene-phosphinidene adduct [(IPr)PH] (1, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were prepared by its reaction with dimeric complexes of the type [LMCl2]2, which afforded the three-legged piano-stool complexes [LMCl2{HP(IPr)}] (9a/9b: M = Ru/Os, L = η6-p-cymene; 10a/10b: M = Rh/Ir, L = η5-C5Me5). Their conversion into the corresponding carbene-phosphinidenide complexes [LMCl{P(IPr)}] (11a/11b: M = Ru/Os; 12a/12b: M = Rh/Ir) with a two-legged piano stool geometry was studied by NMR spectroscopy in the presence of the strong base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Alternatively, the complexes 11 and 12 were isolated in high yields from the reactions of the carbene-phosphinidene adduct [(IPr)PTMS] (2) with [LMCl2]2, whereby formation of the metal-phosphorus bonds was accompanied by elimination of trimethylsilyl chloride (Me3SiCl). Theoretical calculations reveal a strong polarization of the phosphorus ligands upon metal complexation, which can be ascribed to the ability of the imidazole moiety to effectively stabilize a positive charge. Dehydrohalogenation of complexes 9/10 to 11/12 affords a significant increase of the metal-phosphorus bond order, with the carbene-phosphinidenide ligand acting as a strong 2σ,2π-electron donor.

16.
Angew Chem Int Ed Engl ; 56(4): 1135-1140, 2017 01 19.
Article in English | MEDLINE | ID: mdl-27996186

ABSTRACT

The reaction of the 2-(trimethylsilyl)imidazolium triflate 9 with diarylboron halides (4-R-C6 H4 )2 BX (R=H, X=Br; R=CH3 , X=Cl; R=CF3 , X=Cl) afforded the NHC-stabilized borenium cations 10 a-c. Cyclic voltammetry revealed a linear correlation between the Hammett parameter σp of the para substituent and the half-wave potential. Chemical reduction with decamethylcobaltocene, [(C5 Me5 )2 Co], furnished the corresponding radicals 11 a-c; their characterization by EPR spectroscopy confirmed the paramagnetic character of 11 a-c, with large hyperfine coupling constants to the boron isotopes 11 B and 10 B, while delocalization of the unpaired electron into the NHC is negligible. DFT calculations of the percentage of spin density distribution between the carbene (NHC) and the boryl fragments (BR2 ) revealed for 11 a-c a spin density ratio (BR2 /NHC) of ca. 9:1, which underlines their distinct boryl radical character. The molecular structure of the most stable species 11 c was established by X-ray diffraction analysis.

17.
Inorg Chem ; 54(24): 12032-45, 2015 Dec 21.
Article in English | MEDLINE | ID: mdl-26652203

ABSTRACT

The bis(imidazolin-2-imine) ligand N,N'-bis(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)-1,1'-ferrocenediamine, fc(NIm)2 (1) was prepared. Its reaction with [NiCl2(dme)] (dme = 1,2-dimethoxyethane) or [PdCl2(MeCN)2] afforded the tetrahedral, paramagnetic complex [(1-κ(2)N,N')NiCl2] (6a) or the diamagnetic, square-planar complex [(1-κ(2)N,N')PdCl2] (6b), respectively. For the latter, slow rearrangement to the ionic complex [(1-κFe,κ(2)N,N')PdCl]Cl, [7]Cl, was observed, which was followed by (1)H NMR and UV/vis spectroscopy. Treatment of [7]Cl with NaBF4 afforded [7]BF4; the palladium atoms in both cations adopt square-planar environments with short Fe-Pd bonds (ca. 2.65 Å). In addition, a series of dicationic complexes of the type [(1-κFe,κ(2)N,N')ML](BF4)2 (8a: M = Ni, L = MeCN; 8b: M = Pd, L = MeCN; 9a: M = Ni, L = PMe3; 9b: M = Pd, L = PMe3) was prepared from 6a (M = Ni) or [7]BF4 by chloride abstraction with NaBF4 or AgBF4 in the presence of acetonitrile or trimethylphosphine, respectively. In the presence of triphenylphosphine, the palladium(II) complex [(1-κFe,κ(2)N,N')Pd(PPh3)](BF4)2 (10) was isolated. Iron-nickel and iron-palladium bonding in these complexes was studied experimentally by NMR, UV/vis, and Mössbauer spectroscopy and by cyclic voltammetry. Detailed DFT calculations were carried out for the cations [(1-κFe,κ(2)N,N')M(MeCN)](2+) in the 8a/8b couple, with Bader's atoms in molecules theory revealing the presence of noncovalent, closed-shell metal-metal interactions. Potential energy surface scans with successive elongation of the Fe-M bonds allow an estimation of the iron-metal bond dissociation energies (BDE) as BDE(Fe-Ni) = 11.3 kcal mol(-1) and BDE(Fe-Pd) = 24.3 kcal mol(-1).

18.
Chemistry ; 21(45): 16178-89, 2015 Nov 02.
Article in English | MEDLINE | ID: mdl-26365325

ABSTRACT

Coinage metal complexes of the N-heterocyclic carbene-phosphinidene adduct IPr⋅PPh (IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were prepared by its reaction with CuCl, AgCl, and [(Me2 S)AuCl], which afforded the monometallic complexes [(IPr⋅PPh)MCl] (M=Cu, Ag, Au). The reaction with two equivalents of the metal halides gave bimetallic [(IPr⋅PPh)(MCl)2 ] (M=Cu, Au); the corresponding disilver complex could not be isolated. [(IPr⋅PPh)(CuOTf)2 ] was prepared by reaction with copper(I) trifluoromethanesulfonate. Treatment of [(IPr⋅PPh)(MCl)2 ] (M=Cu, Au) with Na(BAr(F) ) or AgSbF6 afforded the tetranuclear complexes [(IPr⋅PPh)2 M4 Cl2 ]X2 (X=BAr(F) or SbF6 ), which contain unusual eight-membered M4 Cl2 P2 rings with short cuprophilic or aurophilic contacts along the chlorine-bridged M⋅⋅⋅M axes. Complete chloride abstraction from [(IPr⋅PPh)(AuCl)2 ] was achieved with two equivalents of AgSbF6 in the presence of tetrahydrothiophene (THT) to form [(IPr⋅PPh){Au(THT)}2 ][SbF6 ]2 . The cationic tetra- and dinuclear complexes were used as catalysts for enyne cyclization and carbene transfer reactions.

19.
Dalton Trans ; 44(20): 9400-8, 2015 May 28.
Article in English | MEDLINE | ID: mdl-25912291

ABSTRACT

The reaction of the N-heterocyclic carbene 1,3-di-tert-butyl-4,5-dimethylimidazolin-2-ylidene () with trimethylsilyl iodide, triflate and triflimidate [Me3SiX, X = I, CF3SO3 (OTf), (CF3SO2)2N (NTf2)] by mixing the neat, liquid starting materials afforded the corresponding 2-(trimethylsilyl)imidazolium salts [()SiMe3]X as highly reactive, white crystalline solids. Only the triflimidate (X = NTf2) proved to be stable in solution and could be characterized by means of NMR spectroscopy (in C6D5Br) and X-ray diffraction analysis, whereas dissociation into free and Me3SiOTf was observed for the triflate system, in agreement with the trend derived by DFT calculations; the iodide was too insoluble for characterization. The compounds [()SiMe3]X showed the reactivity expected for frustrated carbene-silylium pairs, and treatment with carbon dioxide, tert-butyl isocyanate and diphenylbutadiyne gave the 1,2-addition products [()CO2SiMe3]X (X = I, OTf, NTf2), [()C(NtBu)OSiMe3]OTf and [()C(Ph)C(SiMe3)CCPh]OTf, respectively. Upon reaction with [AuCl(PPh3)], metal-chloride bond activation was observed, with formation of the cationic gold(i) complexes [()Au(PPh3)]X (X = OTf, NTf2).

20.
Dalton Trans ; 44(26): 11717-24, 2015 Jul 14.
Article in English | MEDLINE | ID: mdl-25881562

ABSTRACT

Bis(η(5)-2,4-dimethylpentadienyl)ruthenium(II), [(η(5)-C7H11)2Ru] (1, "open ruthenocene"), which has become accessible in high yield and large quantities via an isoprene-derived diallyl ruthenium(IV) complex, can be converted into the protonated open ruthenocene 2 by treatment with HBF4 and subsequently into the protonated half-open ruthenocene 3 by reaction with cyclopentadiene. The electronic structure of 3 was studied by DFT methods, revealing that the CH-agostic complex [(η(5)-C5H5)Ru{(1-4η)-C7H12-η(2)-C(5),H(5)}]BF4 (A) represents the global minimum, which is 3.7 kcal mol(−1) lower in energy than the hydride complex [(η(5)-C5H5)RuH(η(5)-C7H11)]BF4 (B). 2 and 3 were treated with the ligands N,N'-bis(1,3,4,5-tetramethylimidazolin-2-ylidene)-1,2-ethanediamine (BL(Me)) and N,N'-bis(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)-1,2-ethanediamine (BL(iPr)) to afford the cationic 16-electron pentadienyl and cyclopentadienyl complexes [(η(5)-C7H11)Ru(BL(R))]BF4 (4a, R = Me; 4b, R = iPr) and [(η(5)-C5H5)Ru(BL(R))]BF4 (5a, R = Me; 5b, R = iPr). All complexes catalyse the transfer hydrogenation of acetophenone in isopropanol, and the most active complex 4a in this reaction was employed for the hydrogenation of a broader range of aliphatic and aromatic ketones.

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