FBpin and its adducts and their role in catalytic borylations.

We present herein investigations concerning the reactivity of B2pin2 and FBpin (pin = pinacolato) with respect to fluoride ions and NHCs (NHC = N-Heterocyclic Carbene) in order to understand better the role of added fluoride in our recently reported Ni-catalyzed C-F borylation process, to confirm the nature of the NHC-adducts of FBpin, and to explain the formation of the species detected as side products of the defluoroborylation reaction. We report the calculated gas phase fluoride ion affinities (FIA) of relevant boron species and demonstrate that the presence of one equivalent of added F- in solution will bind and activate B2pin2 (FIA = +247 kJ mol-1), but it will also bind even more effectively to FBpin (FIA = +287 kJ mol-1) formed in the reaction. We prepared the NHC-adducts of FBpin by two different methods and isolated and characterized several examples of the type FBpin·NHC (NHC = iPr2Im, 1; Me2Im, 2; MeiPrIm, 3; nPr2Im, 4; Mes2Im 5). The salts [pinBF2][NMe4] 6, as well as the significantly more soluble analogue [pinBF2][NnBu4] 7, were also isolated and characterized, providing confirmation of the presence of the pinBF2 anion in various stoichiometric and catalytic borylation reactions.

Reactivity of NHC Alane Adducts towards N-Heterocyclic Carbenes and Cyclic (Alkyl)(amino)carbenes: Ring Expansion, Ring Opening, and Al-H Bond Activation.

The synthesis of mono-NHC alane adducts of the type (NHC)⋅AlH3 (NHC=Me2 Im (1), Me2 ImMe (2), iPr2 Im (3 and [D3 ]-3), iPr2 ImMe (4), Dipp2 Im (10); Im=imidazolin-2-ylidene, Dipp=2,6-diisopropylphenyl) and (NHC)⋅AliBu2 H (NHC=iPr2 Im (11), Dipp2 Im (12)) as well as their reactivity towards different types of carbenes is presented. Although the mono-NHC adducts remained stable at elevated temperatures, ring expansion occurred when (iPr2 Im)⋅AlH3 (3) was treated with a second equivalent of the carbene iPr2 Im to give (iPr2 Im)⋅AlH(RER-iPr2 ImH2 ) (6). In 6, {(iPr2 Im}AlH} is inserted into the NHC ring. In contrast, ring opening was observed with the sterically more demanding Dipp2 Im with the formation of (iPr2 Im)⋅AlH2 (ROR-Dipp2 ImH2 )H2 Al⋅(iPr2 Im) (9). In 9, two {(iPr2 Im)⋅AlH2 } moieties stabilize the ring-opened Dipp2 Im. If two hydridic sites are blocked, the adducts are stable with respect to further ring expansion or ring opening, as exemplified by the adducts (iPr2 Im)⋅AliBu2 H (11) and (Dipp2 Im)⋅AliBu2 H (12). The adducts (NHC)⋅AlH3 and (iPr2 Im)⋅AliBu2 H reacted with cAACMe by insertion of the carbene carbon atom into the Al-H bond to give (NHC)⋅AlH2 /iBu2 (cAACMe H) (13-18) instead of ligand substitution, ring-expansion, or ring-opened products.

Iron(II), Cobalt(II), Nickel(II), and Zinc(II) Silylene Complexes: Reaction of the Silylene [iPrNC(NiPr2 )NiPr]2 Si with FeBr2 , CoBr2 , NiBr2 ⋠MeOCH2 CH2 OMe, ZnCl2 , and ZnBr2.

Reaction of the donor-stabilized silylene [iPrNC(NiPr2 )NiPr]2 Si (1) with FeBr2 , CoBr2 , NiBr2 ⋅MeOCH2 CH2 OMe, ZnCl2 , and ZnBr2 afforded the respective transition-metal silylene complexes 4-8, the formation of which can be described in terms of a Lewis acid/base reaction (4, 5, 7, 8) or a nucleophilic substitution reaction (6). However, the reactivity profile of silylene 1 is not only based on its strong Lewis base character; the different coordination modes of the two guanidinato ligands (4-6 vs. 7 and 8) add an additional reactivity facet. The paramagnetic compounds 4 and 5 and the diamagnetic compounds 6⋅THF, 7, and 8⋅0.5 Et2 O were structurally characterized by single-crystal X-ray diffraction. In addition, compound 6⋅THF was studied by 15 N and 29 Si solid-state NMR spectroscopy, and 7 and 8 were characterized by NMR spectroscopic studies in the solid state (15 N, 29 Si) and in solution (1 H, 13 C, 29 Si). Compounds 4-8 represent very rare examples of FeII , CoII , NiII , and ZnII silylene complexes. Four-coordinate silicon(II) compounds with an SiN3 M skeleton (M=Fe, Co, Ni) and M in the formal oxidation state +2 (4-6) have not yet been reported, and five-coordinate silicon(II) compounds with an SiN4 Zn skeleton (7, 8) are also unprecedented.

Electronic Structure and Excited-State Dynamics of an Arduengo-Type Carbene and its Imidazolone Oxidation Product.

We describe an investigation of the excited-state dynamics of isolated 1,3-di-tert-butyl-imidazoline-2-ylidene (tBu2 Im, C11 H20 N2 , m/z=180), an Arduengo-type carbene, by time- and frequency-resolved photoionization using a picosecond laser system. The energies of several singlet and triplet excited states were calculated by time-dependent density functional theory (TD-DFT). The S1 state of the carbene deactivates on a 100 ps time scale possibly by intersystem crossing. In the experiments we observed an additional signal at m/z=196, that was assigned to the oxidation product 1,3-di-tert-butyl-imidazolone, tBu2 ImO. It shows a well-resolved resonance-enhanced multiphoton ionization (REMPI) spectrum with an origin located at 36951 cm-1 . Several low-lying vibrational bands could be assigned, with a lifetime that depends strongly on the excitation energy. At the origin the lifetime is longer than 3 ns, but drops to 49 ps at higher excess energies. To confirm formation of the imidazolone we also performed experiments on benzimidazolone (BzImO) for comparison. Apart from a redshift for BzImO the spectra of the two compounds are very similar. The TD-DFT values display a very good agreement with the experimental data.

Adduct Formation, B-H Activation and Ring Expansion at Room Temperature from Reactions of HBcat with NHCs.

We report the reactions of catecholborane (HBcat; 1) with unsaturated and saturated NHCs as well as CAAC(Me) . Mono-NHC adducts of the type HBcat⋅NHC (NHC=nPr2 Im, iPr2 Im, iPr2 Im(Me) , and Dipp2 Im) were obtained by stoichiometric reactions of HBcat with the unsaturated NHCs. The reaction of CAAC(Me) with HBcat yielded the B-H activated product CAAC(Me) (H)Bcat via insertion of the carbine-carbon atom into the B-H bond. The saturated NHC Dipp2 SIm reacted in a 2:2 ratio yielding an NHC ring-expanded product at room temperature forming a six-membered -B-C=N-C=C-N- ring via C-N bond cleavage and further migration of the hydrides from two HBcat molecules to the former carbene-carbon atom.

A facile route to backbone-tethered N-heterocyclic carbene (NHC) ligands via NHC to aNHC rearrangement in NHC silicon halide adducts.

The reaction of 1,3-diisopropylimidazolin-2-ylidene (iPr2 Im) with diphenyldichlorosilane (Ph2 SiCl2 ) leads to the adduct (iPr2 Im)SiCl2 Ph2 1. Prolonged heating of isolated 1 at 66 °C in THF affords the backbone-tethered bis(imidazolium) salt [((a) HiPr2 Im)2 SiPh2 ](2+) 2 Cl(-) 2 ("(a) " denotes "abnormal" coordination of the NHC), which can be synthesized in high yields in one step starting from two equivalents of iPr2 Im and Ph2 SiCl2 . Imidazolium salt 2 can be deprotonated in THF at room temperature using sodium hydride as a base and catalytic amounts of sodium tert-butoxide to give the stable N-heterocyclic dicarbene ((a) iPr2 Im)2 SiPh2 3, in which two NHCs are backbone-tethered with a SiPh2 group. This easy-to-synthesize dicarbene 3 can be used as a novel ligand type in transition metal chemistry for the preparation of dinuclear NHC complexes, as exemplified by the synthesis of the homodinuclear copper(I) complex [{(a) (ClCuiPr2 Im)}2 SiPh2 ] 4.

Monomeric Chiral and Achiral Basket-Handle Porphyrins: Synthesis, Structural Features, and Arrested Tautomerism.

Chiral and achiral basket-handle porphyrins (BHPs) with different p-xylene straps and peripheral solubilizing groups were synthesized using a previously established synthetic approach. Subsequent modification, functionalization, and metalation of the tetrapyrrolic macrocycle yielded more than 80 BHPs. The chiral representatives were resolved into their enantiomers, whose absolute configurations were determined by comparison of their ECD spectra with other experimental or quantum chemically calculated spectra. NMR studies and coupled-cluster calculations proved that the free base BHPs, although highly symmetric, exhibited the phenomenon of "arrested tautomerism". Comparison of the solid-state structures of three metalated BHPs offered detailed insight into their three-dimensional shape. Finally, directly linked dimeric porphyrins with a BHP subunit were synthesized from functionalized BHPs to prove their value as synthetic building blocks.

B-B bond activation and NHC ring-expansion reactions of diboron(4) compounds, and accurate molecular structures of B2(NMe2)4, B2eg2, B2neop2 and B2pin2.

In this detailed study we report on the structures of the widely employed diboron(4) compounds bis(pinacolato)diboron (B2pin2) and bis(neopentyl glycolato)diboron (B2neop2), as well as bis(ethylene glycolato)diboron (B2eg2) and tetrakis(dimethylamino)diboron (B2(NMe2)4), and their reactivity, along with that of bis(catecholato)diboron (B2cat2) with backbone saturated and backbone unsaturared N-heterocyclic carbenes (NHCs) of different steric demand. Depending on the nature of the diboron(4) compound and the NHC used, Lewis-acid/Lewis-base adducts or NHC ring-expansion products stemming from B-B and C-N bond activation have been observed. The corresponding NHC adducts and NHC ring-expanded products were isolated and characterised via solid-state and solution NMR spectroscopy and X-ray diffraction. In general, we observed B-B bond and C-N bond activation at low temperature for B2eg2, at room temperature for B2neop2 and at higher temperature for B2cat2. The reactivity strongly depends on steric effects of the NHCs and the diboron(4) compounds, as well as on the corresponding Lewis-basicity and Lewis-acidity. Our results provide profound insight into the chemistry of these diboron(4) reagents with the nowadays ubiquitous NHCs, the stability of the corresponding NHC adducts and on B-B bond activation using Lewis-bases in general. We demonstrate that B-B bond activation may be triggered even at temperatures as low as -40 °C to -30 °C without any metal species involved. For example, the reactions of B2eg2 with sterically less demanding NHCs such as Me2ImMe and iPr2Im in solution led to the corresponding ring-expanded products at low temperatures. Furthermore, boronium [L2B(OR)2]+ and borenium [LB(OR)2]+ cations have been observed from the reaction of the bis-borate B2eg3 with the NHCs iPr2Im and Me2ImMe, which led to the conclusion that the activation of bis-borates with NHCs (or Lewis-bases in general) might be a facile and simple route to access such species.

The reductive P-P coupling of primary and secondary phosphines mediated by N-heterocyclic carbenes.

The dehydrogenative coupling of primary and secondary phosphines with the N-heterocyclic carbene iPr2Im (1,3-di-isopropyl-imidazolin-2-ylidene) has been reported. The dehydrogenation of R2PH affords diphosphines R2P-PR2. The reaction of iPr2Im with ArPH2 leads to the formation of NHC phosphinidene adducts iPr2Im[double bond, length as m-dash]PAr and cyclic oligophosphines P4Ar4, P5Ar5 and P6Ar6, depending on the stoichiometry used. The NHC acts in these reactions as a phosphine activator and hydrogen acceptor.

Chiral and achiral basket-handle porphyrins: short synthesis and stereostructures of these versatile building blocks.

Both, chiral and achiral basket-handle porphyrins were synthesized via a short, reliable, and efficient route in multigram quantities. Standard synthetic protocols such as metalation of the macrocycle, halogenation, and borylation of the porphyrin core or alkyl- and arylation with lithium organyls were successfully adapted. The planar-chiral representatives were resolved into their enantiomers, whose absolute configurations were determined by comparison of experimental CD spectra with TDCAM-B3LYP calculated ones.