@article{SundermeyerRadiusBurschka1992, author = {Sundermeyer, Joerg and Radius, Udo and Burschka, Christian}, title = {Organometall-Imide - h{\"o}hervalente Derivate der d-Metall-S{\"a}uren, 3. Synthese ond Reaktionen von (Pentamethylcyclopentadienyl)(imido)-Komplexen des Molybd{\"a}ns und Wolframs und eine effiziente Strategie zur Synthese der Organometallate NBu\(_4\)[Cp*MO\(_3\)] (M = Mo, W)}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-31884}, year = {1992}, abstract = {A convenient and new entry into the chemistry of highvalent pentamethylcyclopentadienyl halfsandwich complexes of molybdenum and tungsten is described. The reaction of Mo-(NtBu)\(_2\)Cl\(_2\) or W(NtBu)\(_2\)Cl\(_2\)(py)\(_2\) with Cp*Li (Cp* = \(\eta^5\)-C\(_5\)Me\(_5\)) provides a high-yield route to new complexes Cp*Mo-(NtBu)\(_2\)CI (la) and Cp*W(NtBu)\(_2\)Cl (1 b) which are converted into a variety of diimido, monoimido, and oxo derivatives. Treatment of 1 a, b with MeLi yields the highly volatile methyl derivatives Cp*Mo(NtBu)\(_2\)Me (2a) and Cp*W(NtBu)\(_2\)Me (2b), while protolysis of 1 a, b with an excess of HCI gas leads to selective cleavage of only one imido function with formation of Cp*Mo(NtBu)Cl\(_3\) (3a) and Cp*W(NtBu)Cl\(_3\) (3b). In contrast, protolysis of 1 a, b with aqueous HCI provides a high-yield route to the well-known organometallic oxides [Cp*MoO\(_2\)](μ-0) (4a) and [Cp*WO\(_2\)](\(\mu\)-0) (4b). These two key compounds are easily converted into the organomolybdate and organotungstate salts NBu\(_4\)[Cp*MoO\(_3\)] (5a) and NBu\(_4\)[Cp*WO\(_3\)] (Sb) by cleavage of the M - 0 - M bridge with NBu\(_4\)[OH]. The Xray structure of 3a is reported.}, subject = {Pentamethylcyclopentadienderivate}, language = {de} } @article{LorkowskiKrahfussKubickietal.2019, author = {Lorkowski, Jan and Krahfuß, Mirjam and Kubicki, Maciej and Radius, Udo and Pietraszuk, Cezary}, title = {Intramolecular Ring-Expansion Reaction (RER) and Intermolecular Coordination of In Situ Generated Cyclic (Amino)(aryl)carbenes (cAArCs)}, series = {Chemistry - A European Journal}, volume = {25}, journal = {Chemistry - A European Journal}, number = {48}, doi = {10.1002/chem.201902630}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-212496}, pages = {11365 -- 11374}, year = {2019}, abstract = {Cyclic (amino)(aryl)carbenes (cAArCs) based on the isoindoline core were successfully generated in situ by α-elimination of 3-alkoxyisoindolines at high temperatures or by deprotonation of isoindol-2-ium chlorides with sodium or copper(I) acetates at low temperatures. 3-Alkoxy-isoindolines 2 a,b-OR (R=Me, Et, iPr) have been prepared in high yields by the addition of a solution of 2-aryl-1,1-diphenylisoindol-2-ium triflate (1 a,b-OTf; a: aryl=Dipp=2,6-diisopropylphenyl; b: Mesityl-, Mes=2,4,6-trimethylphenyl) to the corresponding alcohol (ROH) with NEt3 at room temperature. Furthermore, the reaction of 2 a,b-OMe in diethyl ether with a tenfold excess of hydrochloric acid led to the isolation of the isoindol-2-ium chlorides 1 a,b-Cl in high yields. The thermally generated cAArC reacts with sulfur to form the thioamide 3 a. Without any additional trapping reagent, in situ generation of 1,1-diphenylisoidolin-3-ylidenes does not lead to the isolation of these compounds, but to the reaction products of the insertion of the carbene carbon atom into an ortho C-H bond of a phenyl substituent, followed by ring-expansion reaction; namely, anthracene derivatives 9-N(H)aryl-10-Ph-C14H8 4 a,b (a: Dipp; b: Mes). These compounds are conveniently synthesized by deprotonation of the isoindol-2-ium chlorides with sodium acetate in high yields. Deprotonation of 1 a-Cl with copper(I) acetate at low temperatures afforded a mixture of 4 a and the corresponding cAArC copper(I) chloride 5 a, and allowed the isolation and structural characterization of the first example of a cAArC copper complex of general formula [(cAArC)CuCl].}, language = {en} } @article{BudimanFriedrichRadiusetal.2019, author = {Budiman, Yudha P. and Friedrich, Alexandra and Radius, Udo and Marder, Todd B.}, title = {Copper-catalysed Suzuki-Miyaura cross-coupling of highly fluorinated aryl boronate esters with aryl iodides and bromides and fluoroarene-arene π-stacking interactions in the products}, series = {ChemCatChem}, volume = {11}, journal = {ChemCatChem}, number = {21}, doi = {10.1002/cctc.201901220}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-204839}, pages = {5387-5396}, year = {2019}, abstract = {A combination of copper iodide and phenanthroline as the ligand is an efficient catalyst for Suzuki-Miyaura cross-coupling of highly fluorinated boronate esters (aryl-Bpin) with aryl iodides and bromides to generate fluorinated biaryls in good to excellent yields. This method represents a nice alternative to traditional cross-coupling methods which require palladium catalysts and stoichiometric amounts of silver oxide. We note that π⋅⋅⋅π stacking interactions dominate the molecular packing in the partly fluorinated biaryl crystals investigated herein. They are present either between the arene and perfluoroarene, or solely between arenes or perfluoroarenes, respectively.}, language = {en} } @article{LorkowskiKrahfussKubickietal.2019, author = {Lorkowski, Jan and Krahfuss, Mirjam and Kubicki, Maciej and Radius, Udo and Pietraszuk, Cezary}, title = {Intramolecular ring expansion reaction (RER) and intermolecular coordination of in situ generated Cyclic (Amino)(Aryl)Carbenes (cAArCs)}, series = {Chemistry - A European Journal}, volume = {25}, journal = {Chemistry - A European Journal}, number = {48}, doi = {10.1002/chem.201902630}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-204847}, pages = {11365-11374}, year = {2019}, abstract = {Cyclic (amino)(aryl)carbenes (cAArCs) based on the isoindoline core were successfully generated in situ by α-elimination of 3-alkoxyisoindolines at high temperatures or by deprotonation of isoindol-2-ium chlorides with sodium or copper(I) acetates at low temperatures. 3-Alkoxy-isoindolines 2 a ,b-OR (R=Me, Et, i Pr) have been prepared in high yields by the addition of a solution of 2-aryl-1,1-diphenylisoindol-2-ium triflate (1 a ,b-OTf ; a : aryl=Dipp=2,6-diisopropylphenyl; b : Mesityl-, Mes=2,4,6-trimethylphenyl) to the corresponding alcohol (ROH) with NEt3 at room temperature. Furthermore, the reaction of 2 a ,b-OMe in diethyl ether with a tenfold excess of hydrochloric acid led to the isolation of the isoindol-2-ium chlorides 1 a ,b-Cl in high yields. The thermally generated cAArC reacts with sulfur to form the thioamide 3 a . Without any additional trapping reagent, in situ generation of 1,1-diphenylisoidolin-3-ylidenes does not lead to the isolation of these compounds, but to the reaction products of the insertion of the carbene carbon atom into an ortho C-H bond of a phenyl substituent, followed by ring-expansion reaction; namely, anthracene derivatives 9-N(H)aryl-10-Ph-C14H8 4 a ,b (a : Dipp; b : Mes). These compounds are conveniently synthesized by deprotonation of the isoindol-2-ium chlorides with sodium acetate in high yields. Deprotonation of 1 a-Cl with copper(I) acetate at low temperatures afforded a mixture of 4 a and the corresponding cAArC copper(I) chloride 5 a , and allowed the isolation and structural characterization of the first example of a cAArC copper complex of general formula [(cAArC)CuCl].}, language = {en} } @article{LiuBudimanTianetal.2020, author = {Liu, Zhiqiang and Budiman, Yudha P. and Tian, Ya-Ming and Friedrich, Alexandra and Huang, Mingming and Westcott, Stephen A. and Radius, Udo and Marder, Todd B.}, title = {Copper-Catalyzed Oxidative Cross-Coupling of Electron-Deficient Polyfluorophenylboronate Esters with Terminal Alkynes}, series = {Chemistry - A European Journal}, volume = {26}, journal = {Chemistry - A European Journal}, number = {71}, doi = {10.1002/chem.202002888}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-224362}, pages = {17267 -- 17274}, year = {2020}, abstract = {We report herein a mild procedure for the copper-catalyzed oxidative cross-coupling of electron-deficient polyfluorophenylboronate esters with terminal alkynes. This method displays good functional group tolerance and broad substrate scope, generating cross-coupled alkynyl(fluoro)arene products in moderate to excellent yields. Thus, it represents a simple alternative to the conventional Sonogashira reaction.}, language = {en} } @article{HorrerKrahfussLubitzetal.2020, author = {Horrer, G{\"u}nther and Krahfuß, Mirjam J. and Lubitz, Katharina and Krummenacher, Ivo and Braunschweig, Holger and Radius, Udo}, title = {N-Heterocyclic Carbene and Cyclic (Alkyl)(amino)carbene Complexes of Titanium(IV) and Titanium(III)}, series = {European Journal of Inorganic Chemistry}, volume = {2020}, journal = {European Journal of Inorganic Chemistry}, number = {3}, doi = {10.1002/ejic.201901207}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-208725}, pages = {281-291}, year = {2020}, abstract = {The reaction of one and two equivalents of the N -heterocyclic carbene IMes [IMes = 1,3-bis(2,4,6-trimethyl-phenyl)imidazolin-2-ylidene] or the cyclic (alkyl)(amino)carbene cAAC\(^{Me}\) [cAAC\(^{Me}\) = 1-(2,6-diisopropyl-phenyl)-3,3,5,5-tetra-methylpyrrolidin-2-ylidene] with [TiCl\(_{4}\)] in n -hexane results in the formation of mono- and bis-carbene complexes [TiCl\(_{4}\)(IMes)] 1 , [TiCl\(_{4}\)(IMes)2] 2 , [TiCl\(_{4}\)(cAAC\(^{Me}\))] 3 , and [TiCl\(_{4}\)(cAAC\(^{Me}\))\(_{2}\)] 4 , respectively. For comparison, the titanium(IV) NHC complex [TiCl\(_{4}\)(Ii Pr\(^{Me}\))] 5 (Ii Pr\(^{Me}\) = 1,3-diisopropyl-4,5-dimethyl-imidazolin-2-ylidene) has been synthesized and structurally characterized. The reaction of [TiCl\(_{4}\)(IMes)] 1 with PMe\(_{3}\) affords the mixed substituted complex [TiCl\(_{4}\)(IMes)(PMe\(_{3}\))] 6 . The reactions of [TiCl\(_{3}\)(THF)\(_{3}\)] with two equivalents of the carbenes IMes and cAAC\(^{Me}\) in n -hexane lead to the clean formation of the titanium(III) complexes [TiCl\(_{3}\)(IMes)\(_{2}\)] 7 and [TiCl\(_{3}\)(cAAC\(^{Me}\))\(_{2}\)] 8 . Compounds 1 -8 have been completely characterized by elemental analysis, IR and multinuclear NMR spectroscopy and for 2 -5 , 7 and 8 by X-ray diffraction. Magnetometry in solution, EPR and UV/Vis spectroscopy and DFT calculations performed on 7 and 8 are indicative of a predominantly metal-centered d\(^{1}\)-radical in both cases.}, language = {en} } @article{TenderaSchaubKrahfussetal.2020, author = {Tendera, Lukas and Schaub, Thomas and Krahfuss, Mirjam J. and Kuntze-Fechner, Maximilian W. and Radius, Udo}, title = {Large vs. Small NHC Ligands in Nickel(0) Complexes: The Coordination of Olefins, Ketones and Aldehydes at [Ni(NHC)\(_{2}\)]}, series = {European Journal of Inorganic Chemistry}, volume = {2020}, journal = {European Journal of Inorganic Chemistry}, number = {33}, doi = {10.1002/ejic.202000493}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-216058}, pages = {3194 -- 3207}, year = {2020}, abstract = {Investigations concerning the reactivity of Ni(0) complexes [Ni(NHC)\(_{2}\)] of NHCs (N-heterocyclic carbene) of different steric demand, Mes\(_{2}\)Im (= 1,3-dimesitylimidazoline-2-ylidene) and iPr\(_{2}\)Im (= 1,3-diisopropyl-imidazoline-2-ylidene), with olefins, ketones and aldehydes are reported. The reaction of [Ni(Mes\(_{2}\)Im)\(_{2}\)] 1 with ethylene or methyl acrylate afforded the complexes [Ni(Mes\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-C\(_{2}\)H\(_{4}\))] 3 and [Ni(Mes\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-(C,C)-H\(_{2}\)C=CHCOOMe)] 4, as it was previously reported for [Ni\(_{2}\)(iPr\(_{2}\)Im)\(_{4}\)(µ-(η\(^{2}\):η\(^{2}\))-COD)] 2 as a source for [Ni(iPr\(_{2}\)Im)\(_{2}\)]. In contrast to 2, complex 1 does not react with sterically more demanding olefins such as tetramethylethylene, 1,1-diphenylethylene and cyclohexene. The reaction of [Ni(NHC)\(_{2}\)] with more π-acidic ketones or aldehydes led to formation of complexes with side-on η\(^{2}\)-(C,O)-coordinating ligands: [Ni(iPr\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=CH\(^{t}\)Bu)] 5, [Ni(iPr\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=CHPh)] 6, [Ni(iPr\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=CMePh)] 7, [Ni(iPr\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=CPh\(_{2}\))] 8, [Ni(iPr\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=C(4-F-C\(_{6}\)H\(_{4}\))\(_{2}\))] 9, [Ni(iPr\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=C(OMe)(CF\(_{3}\)))] 10 and [Ni(Mes\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=CHPh)] 11, [Ni(Mes\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=CH(CH(CH\(_{3}\))\(_{2}\)))] 12, [Ni(Mes\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=CH(4-NMe\(_{2}\)-C\(_{6}\)H\(_{4}\)))] 13, [Ni(Mes\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=CH(4-OMe-C\(_{6}\)H\(_{4}\)))] 14, [Ni(Mes\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=CPh\(_{2}\))] 15 and [Ni(Mes\(_{2}\)Im)\(_{2}\)(η\(^{2}\)-O=C(4-F-C\(_{6}\)H\(_{4}\))\(_{2}\))] 16. The reaction of 1 and 2 with these simple aldehydes and ketones does not lead to a significantly different outcome, but NHC ligand rotation is hindered for the Mes\(_{2}\)Im complexes 3, 4 and 11-16 according to NMR spectroscopy. The solid-state structures of 3, 4, 11 and 12 reveal significantly larger C\(_{NHC}\)-Ni-C\(_{NHC}\) angles in the Mes\(_{2}\)Im complexes compared to the iPr\(_{2}\)Im complexes. As electron transfer in d\(^{8}\)- (or d\(^{10}\)-) ML\(_{2}\) complexes to π-acidic ligands depends on the L-M-L bite angle, the different NHCs lead thus to a different degree of electron transfer and activation of the olefin, aldehyde or ketone ligand, i.e., [Ni(iPr\(_{2}\)Im)\(_{2}\)] is the better donor to these π-acidic ligands. Furthermore, we identified two different side products from the reaction of 1 with benzaldehyde, trans-[Ni(Mes\(_{2}\)Im)\(_{2}\)H(OOCPh)] 17 and [Ni\(_{2}\)(Mes\(_{2}\)Im)\(_{2}\)(µ\(_{2}\)-CO)(µ\(_{2}\)-η\(^{2}\)-C,O-PhCOCOPh)] 18, which indicate that radical intermediates and electron transfer processes might be of importance in the reaction of 1 with aldehydes and ketones.}, language = {en} } @article{HockWernerRiethmannetal.2020, author = {Hock, Andreas and Werner, Luis and Riethmann, Melanie and Radius, Udo}, title = {Bis-NHC Aluminium and Gallium Dihydride Cations [(NHC)\(_{2}\)EH\(_{2}\)]\(^{+}\) (E = Al, Ga)}, series = {European Journal of Inorganic Chemistry}, volume = {2020}, journal = {European Journal of Inorganic Chemistry}, number = {42}, doi = {10.1002/ejic.202000720}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-217928}, pages = {4015 -- 4023}, year = {2020}, abstract = {The NHC alane and gallane adducts (NHC)·AlH\(_{2}\)I (NHC = Me\(_{2}\)Im\(^{Me}\) 7, iPr\(_{2}\)Im 8, iPr\(_{2}\)Im\(^{Me}\) 9) and (NHC)·GaH\(_{2}\)I (NHC = Me\(_{2}\)Im\(^{Me}\) 10, iPr\(_{2}\)Im\(^{Me}\) 11, Dipp\(_{2}\)Im 12; R\(_{2}\)Im = 1,3-di-organyl-imidazolin-2-ylidene; Dipp = 2,6-diisopropylphenyl; iPr = isopropyl; Me\(_{2}\)Im\(^{Me}\) = 1,3,4,5-tetra-methyl-imidazolin-2-ylidene) were prepared either by the simple yet efficient reaction of the NHC adduct (NHC)·AlH\(_{3}\) with elemental iodine or by the treatment of (NHC)·GaH\(_{3}\) with an excess of methyl iodide at room temperature. The reaction of one equivalent of the group 13 NHC complexes with an additional equivalent of the corresponding NHC afforded cationic aluminium and gallium hydrides [(NHC)\(_{2}\)·AlH\(_{2}\)]\(^{+}\)I- (NHC = Me\(_{2}\)Im\(^{Me}\) 13, iPr\(_{2}\)Im 14, iPr\(_{2}\)Im\(^{Me}\) 15) and [(NHC)\(_{2}\)·GaH\(_{2}\)]\(^{+}\)I- (NHC = Me\(_{2}\)Im\(^{Me}\) 16, iPr\(_{2}\)Im\(^{Me}\) 17) and the normal and abnormal NHC coordinated compound [(Dipp\(_{2}\)Im)·GaH\(_{2}\)(aDipp\(_{2}\)Im)]+I- 18. Compounds 7-18 were isolated and characterized by means of elemental analysis, IR and multinuclear NMR spectroscopy and by X-ray diffraction of the compounds 7, 9, 10, 15, 16 and 18.}, language = {en} } @article{LiuMingLuoetal.2020, author = {Liu, Xiaocui and Ming, Wenbo and Luo, Xiaoling and Friedrich, Alexandra and Maier, Jan and Radius, Udo and Santos, Webster L. and Marder, Todd B.}, title = {Regio- and Stereoselective Synthesis of 1,1-Diborylalkenes via Br{\o}nsted Base-Catalyzed Mixed Diboration of Alkynyl Esters and Amides with BpinBdan}, series = {European Journal of Organic Chemistry}, volume = {2020}, journal = {European Journal of Organic Chemistry}, number = {13}, doi = {10.1002/ejoc.202000128}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-214728}, pages = {1941 -- 1946}, year = {2020}, abstract = {The NaOtBu-catalyzed mixed 1,1-diboration of terminal alkynes using the unsymmetrical diboron reagent BpinBdan (pin = pinacolato; dan = 1,8-diaminonaphthalene) proceeds in a regio- and stereoselective fashion affording moderate to high yields of 1,1-diborylalkenes bearing orthogonal boron protecting groups. It is applicable to gram-scale synthesis without loss of yield or selectivity. The mixed 1,1-diborylalkene products can be utilized in Suzuki-Miyaura cross-coupling reactions which take place selectivly at the C-B site. DFT calculations suggest the NaOtBu-catalyzed mixed 1,1-diboration of alkynes occurs through deprotonation of the terminal alkyne, stepwise addition of BpinBdan to the terminal carbon followed by protonation with tBuOH. Experimentally observed selective formation of (Z)-diborylalkenes is supported by our theoretical studies.}, language = {en} } @article{FoehrenbacherKrahfussZapfetal.2021, author = {F{\"o}hrenbacher, Steffen A. and Krahfuss, Mirjam J. and Zapf, Ludwig and Friedrich, Alexandra and Ignat'ev, Nikolai V. and Finze, Maik and Radius, Udo}, title = {Tris(pentafluoroethyl)difluorophosphorane: a versatile fluoride acceptor for transition metal chemistry}, series = {Chemistry Europe}, volume = {27}, journal = {Chemistry Europe}, number = {10}, doi = {10.1002/chem.202004885}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256665}, pages = {3504-3516}, year = {2021}, abstract = {Fluoride abstraction from different types of transition metal fluoride complexes [L\(_n\)MF] (M=Ti, Ni, Cu) by the Lewis acid tris(pentafluoroethyl)difluorophosphorane (C\(_2\)F\(_5\))\(_3\)PF\(_2\) to yield cationic transition metal complexes with the tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C\(_2\)F\(_5\))\(_3\)PF\(_3\)]\(^-\)) is reported. (C\(_2\)F\(_5\))\(_3\)PF\(_2\) reacted with trans-[Ni(iPr\(_2\)Im)\(_2\)(Ar\(^F\))F] (iPr2Im=1,3-diisopropylimidazolin-2-ylidene; Ar\(^F\)=C\(_6\)F\(_5\), 1 a; 4-CF\(_3\)-C\(_6\)F\(_4\), 1 b; 4-C\(_6\)F\(_5\)-C\(_6\)F\(_4\), 1 c) through fluoride transfer to form the complex salts trans-[Ni(iPr\(_2\)Im)\(_2\)(solv)(Ar\(^F\))]FAP (2 a-c[solv]; solv=Et\(_2\)O, CH\(_2\)Cl\(_2\), THF) depending on the reaction medium. In the presence of stronger Lewis bases such as carbenes or PPh\(_3\), solvent coordination was suppressed and the complexes trans-[Ni(iPr\(_2\)Im)\(_2\)(PPh\(_3\))(C\(_6\)F\(_5\))]FAP (trans-2 a[PPh\(_3\)]) and cis-[Ni(iPr\(_2\)Im)\(_2\)(Dipp\(_2\)Im)(C\(_6\)F\(_5\))]FAP (cis-2 a[Dipp\(_2\)Im]) (Dipp\(_2\)Im=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were isolated. Fluoride abstraction from [(Dipp\(_2\)Im)CuF] (3) in CH\(_2\)Cl\(_2\) or 1,2-difluorobenzene led to the isolation of [{(Dipp\(_2\)Im)Cu}\(_2\)]\(^2\)\(^+\)2 FAP\(^-\) (4). Subsequent reaction of 4 with PPh\(_3\) and different carbenes resulted in the complexes [(Dipp\(_2\)Im)Cu(LB)]FAP (5 a-e, LB=Lewis base). In the presence of C6Me6, fluoride transfer afforded [(Dipp\(_2\)Im)Cu(C\(_6\)Me\(_6\))]FAP (5 f), which serves as a source of [(Dipp\(_2\)Im)Cu)]\(^+\). Fluoride abstraction of [Cp\(_2\)TiF\(_2\)] (7) resulted in the formation of dinuclear [FCp\(_2\)Ti(μ-F)TiCp\(_2\)F]FAP (8) (Cp=η\(^5\)-C\(_5\)H\(_5\)) with one terminal fluoride ligand at each titanium atom and an additional bridging fluoride ligand.}, language = {en} }