Exploiting Organometallic Chemistry to Functionalize Small Cuprous Oxide Colloidal Nanocrystals.

The ligand chemistry of colloidal semiconductor nanocrystals mediates their solubility, band gap, and surface facets. Here, selective organometallic chemistry is used to prepare small, colloidal cuprous oxide nanocrystals and to control their surface chemistry by decorating them with metal complexes. The strategy is demonstrated using small (3-6 nm) cuprous oxide (Cu2O) colloidal nanocrystals (NC), soluble in organic solvents. Organometallic complexes are coordinated by reacting the surface Cu-OH bonds with organometallic reagents, M(C6F5)2, M = Zn(II) and Co(II), at room temperature. These reactions do not disrupt the Cu2O crystallinity or nanoparticle size; rather, they allow for the selective coordination of a specific metal complex at the surface. Subsequently, the surface-coordinated organometallic complex is reacted with three different carboxylic acids to deliver Cu-O-Zn(O2CR') complexes. Selective nanocrystal surface functionalization is established using spectroscopy (IR, 19F NMR), thermal gravimetric analyses (TGA), transmission electron microscopy (TEM, EELS), and X-ray photoelectron spectroscopy (XPS). Photoluminescence efficiency increases dramatically upon organometallic surface functionalization relative to that of the parent Cu2O NC, with the effect being most pronounced for Zn(II) decoration. The nanocrystal surfaces are selectively functionalized by both organic ligands and well-defined organometallic complexes; this synthetic strategy may be applicable to many other metal oxides, hydroxides, and semiconductors. In the future, it should allow NC properties to be designed for applications including catalysis, sensing, electronics, and quantum technologies.

Matched Ligands for Small, Stable Colloidal Nanoparticles of Copper, Cuprous Oxide and Cuprous Sulfide.

This work applies organometallic routes to copper(0/I) nanoparticles and describes how to match ligand chemistries with different material compositions. The syntheses involve reacting an organo-copper precursor, mesitylcopper(I) [CuMes]z (z=4, 5), at low temperatures and in organic solvents, with hydrogen, air or hydrogen sulfide to deliver Cu, Cu2 O or Cu2 S nanoparticles. Use of sub-stoichiometric quantities of protonated ligand (pro-ligand; 0.1-0.2 equivalents vs. [CuMes]z ) allows saturation of surface coordination sites but avoids excess pro-ligand contaminating the nanoparticle solutions. The pro-ligands are nonanoic acid (HO2 CR1 ), 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (HO2 CR2 ) or di(thio)nonanoic acid, (HS2 CR1 ), and are matched to the metallic, oxide or sulfide nanoparticles. Ligand exchange reactions reveal that copper(0) nanoparticles may be coordinated by carboxylate or di(thio)carboxylate ligands, but Cu2 O is preferentially coordinated by carboxylate ligands and Cu2 S by di(thio)carboxylate ligands. This work highlights the opportunities for organometallic routes to well-defined nanoparticles and the need for appropriate ligand selection.

Selective oxo ligand functionalisation and substitution reactivity in an oxo/catecholate-bridged UIV/UIV Pacman complex.

The oxo- and catecholate-bridged UIV/UIV Pacman complex [{(py)UIVOUIV(µ-O2C6H4)(py)}(LA)] A (LA = a macrocyclic "Pacman" ligand; anthracenylene hinge between N4-donor pockets, ethyl substituents on meso-carbon atom of each N4-donor pocket) featuring a bent UIV-O-UIV oxo bridge readily reacts with small molecule substrates to undergo either oxo-atom functionalisation or substitution. Complex A reacts with H2O or MeOH to afford [{(py)UIV(µ-OH)2UIV(µ-O2C6H4)(py)}(LA)] (1) and [{(py)UIV(µ-OH)(µ-OMe)UIV(µ-O2C6H4)(py)}(LA)] (2), respectively, in which the bridging oxo ligand in A is substituted for two bridging hydroxo ligands or one bridging hydroxo and one bridging methoxy ligand, respectively. Alternatively, A reacts with either 0.5 equiv. of S8 or 4 equiv. of Se to provide [{(py)UIV(µ-η2:η2-E2)UIV(µ-O2C6H4)(py)}(LA)] (E = S (3), Se (4)) respectively, in which the [E2]2- ion bridges the two UIV centres. To the best of our knowledge, complex A is the first example of either a d- or f-block bimetallic µ-oxo complex that activates elemental chalcogens. Complex A also reacts with XeF2 or 2 equiv. of Me3SiCl to provide [{(py)UIV(µ-X)2UIV(µ-O2C6H4)(py)}(LA)] (X = F (5), Cl (6)), in which the oxo ligand has been substituted for two bridging halido ligands. Reacting A with either XeF2 or Me3SiCl in the presence of O(Bcat)2 at room temperature forms [{(py)UIV(µ-X)(µ-OBcat)UIV(µ-O2C6H4)(py)}(LA)] (X = F (5A), Cl (6A)), which upon heating to 80 °C is converted to 5 and 6, respectively. In order to probe the importance of the bent UIV-O-UIV motif in A on the observed reactivity, the bis(boroxido)-UIV/UIV complex, [{(py)(pinBO)UIVOUIV(OBpin)(py)}(LA)] (B), featuring a linear UIV-O-UIV bond angle was treated with H2O and Me3SiCl. Complex B reacts with two equiv. of either H2O or Me3SiCl to provide [{(py)HOUIVOUIVOH(py)}(LA)] (7) and [{(py)ClUIVOUIVCl(py)}(LA)] (8), respectively, in which reactions occur preferentially at the boroxido ligands, with the µ-oxo ligand unchanged. The formal UIV oxidation state is retained in all of the products 1-8, and selective reactions at the bridging oxo ligand in A is facilitated by: (1) its highly nucleophilic character which is a result of a non-linear UIV-O-UIV bond angle causing an increase in U-O bond covalency and localisation of the lone pairs of electrons on the µ-oxo group, and (2) the presence of the bridging catecholate ligand, which destabilises a linear oxo-bridging geometry and stabilises the resulting products.

Thermal and Photochemical Reduction and Functionalization Chemistry of the Uranyl Dication, [UVIO2]2.

The uranyl ion, [UVIO2]2+, possesses rigorously trans, strongly covalent, and chemically robust U-oxo groups. However, through the use of anaerobic reaction techniques, both one- and two-electron reductive functionalization of the uranyl oxo groups has been discovered and developed. Prior to 2010, this unusual reactivity centered around the reductive silylation of the uranyl ion which entailed conversion of the oxo ligands into siloxy ligands and reductive metalation of the uranyl oxo with Group 1 and f-block metals. This review surveys the large number of new examples of reductive functionalization of the uranyl ion that have been reported since 2010, including reductive borylation and alumination, metalation with d- or f-block metals, and new examples of reductive silylation. Other examples of oxo-group functionalization of [UVIO2]2+ that do not involve reduction, mainly with Group 1 cations, are also covered, along with new advances in the photochemistry of the uranyl(VI) ion that involve the transient formation of formally uranyl(V) [UVO2]+ ion.

Double uranium oxo cations derived from uranyl by borane or silane reduction.

A new type of double uranium oxo cation [O-U-O-U-O]4+ is prepared by selective oxygen-atom abstraction from macrocyclic uranyl complexes using either boranes or silanes. A significant degree of multiple U[double bond, length as m-dash]O bonding is evident throughout the U2O3 core, but either trans-,cis- or trans-,trans-OUOUO motifs can be isolated as boron- or silicon-capped oxo complexes. Further controlled deoxygenation of the borylated system is also possible.

Axially Symmetric U-O-Ln- and U-O-U-Containing Molecules from the Control of Uranyl Reduction with Simple f-Block Halides.

The reduction of UVI uranyl halides or amides with simple LnII or UIII salts forms highly symmetric, linear, oxo-bridged trinuclear UV /LnIII /UV , LnIII /UIV /LnIII , and UIV /UIV /UIV complexes or linear LnIII /UV polymers depending on the stoichiometry and solvent. The reactions can be tuned to give the products of one- or two-electron uranyl reduction. The reactivity and magnetism of these compounds are discussed in the context of using a series of strongly oxo-coupled homo- and heterometallic poly(f-block) chains to better understand fundamental electronic structure in the f-block.

Synthesis and platinum complexes of an alane-appended 1,1'-bis(phosphino)ferrocene ligand.

An aryldimethylalane-appended analogue of 1,1'-bis(diphenylphosphino)ferrocene, FcPPAl, was prepared, and reaction with [Pt(nb)3 ] (nb=norbornene) afforded [Pt(η(2) -nb)(FcPPAl)] (1). Heating a solution of 1 to 80 °C resulted in crystallization of [{Pt(FcPPAl)}2 ] (2), whereas treatment of 1 with C2 H4 , C2 Ph2 , H2 , or CO provided [PtL(FcPPAl)] [L=C2 H4 (3), C2 Ph2 (4)], [PtH2 (FcPPAl)] (5), and [Pt(CO)(FcPPAl)] (6). In all complexes, the FcPPAl ligand is coordinated through both phosphines and the alane. Whereas 2 adopts a T-shaped geometry at platinum, 3-5 are square-pyramidal, and 6 is distorted square-planar. The hydride and carbonyl complexes feature unusual multicenter bonding involving platinum, aluminum, and a hydride or carbonyl ligand.

Platinum complexes of a borane-appended analogue of 1,1'-bis(diphenylphosphino)ferrocene: flexible borane coordination modes and in situ vinylborane formation.

A bis(phosphine)borane ambiphilic ligand, [Fe(η(5) -C5 H4 PPh2 )(η(5) -C5 H4 PtBu{C6 H4 (BPh2 )-ortho})] (FcPPB), in which the borane occupies a terminal position, was prepared. Reaction of FcPPB with tris(norbornene)platinum(0) provided [Pt(FcPPB)] (1) in which the arylborane is η(3) BCC-coordinated. Subsequent reaction with CO and CNXyl (Xyl=2,6-dimethylphenyl) afforded [PtL(FcPPB)] {L=CO (2) and CNXyl (3)} featuring η(2) BC- and η(1) B-arylborane coordination modes, respectively. Reaction of 1 or 2 with H2 yielded [PtH(µ-H)(FcPPB)] in which the borane is bound to a hydride ligand on platinum. Addition of PhC2 H to [Pt(FcPPB)] afforded [Pt(C2 Ph)(µ-H)(FcPPB)] (5), which rapidly converted to [Pt(FcPPB')] (6; FcPPB'=[Fe(η(5) -C5 H4 PPh2 )(η(5) -C5 H4 PtBu{C6 H4 (BPh-CPh=CHPh-Z)-ortho}]) in which the newly formed vinylborane is η(3) BCC-coordinated. Unlike arylborane complex 1, vinylborane complex 6 does not react with CO, CNXyl, H2 or HC2 Ph at room temperature.

A study of M-X-BR3 (M = Pt, Pd or Rh; X = Cl or I) interactions in square planar ambiphilic ligand complexes: structural, spectroscopic, electrochemical and computational comparisons with borane-free analogues.

Reaction of [PtCl(2)(COD)] and [PtI(2)(COD)] with 2,7-di-tert-butyl-5-diphenylboryl-4-diphenylphosphino-9,9-dimethylthioxanthene (TXPB) afforded square planar [PtCl(2)(TXPB)] (1B) and [PtI(2)(TXPB)] (4B), both of which were crystallographically characterized. Single-crystal X-ray quality crystals were also obtained for [PdCl(2)(TXPB)] (2B; Emslie et al., Organometallics, 2008, 27, 5317) as 2B·2CH(2)Cl(2) and solvent-free 2B. Both the chloro and iodo TXPB complexes exhibit metal-halide-borane bridging interactions similar to those in previously reported [RhCl(CO)(TXPB)] (3B) and [RhI(CO)(TXPB)] (5B) (Emslie et al., Organometallics, 2006, 25, 583 and Inorg. Chem., 2010, 49, 4060). To facilitate a more detailed analysis of M-X-BR(3) (X = Cl and I) interactions, a borane-free analogue of the TXPB ligand, 2,7-di-tert-butyl-4-diphenylphosphino-9,9-dimethylthioxanthene (TXPH), was prepared. Reaction with [PtX(2)(COD)] (X = Cl or I), [PdCl(2)(COD)] and 0.5 [{RhCl(CO)(2)}(2)] provided square planar [PtCl(2)(TXPH)] (1H), [PdCl(2)(TXPH)] (2H), [RhCl(CO)(TXPH)] (3H) and [PtI(2)(TXPH)] (4H). M-Cl-BR(3) and M-I-BR(3) bonding in 1B-5B was then probed through the use of structural comparisons, IR and NMR spectroscopy, cyclic voltammetry, and DFT calculations (Slater-type orbitals, Mayer bond orders, Hirshfeld charges, fragment analysis, SCF deformation density isosurfaces, and energy decomposition analysis).

Acyclic boron-containing π-ligand complexes: η2- and η3-coordination modes.

Cyclic boron-containing π-ligands such as boratabenzenes and borollides are well established, in particular as supporting ligands. By contrast, the chemistry of acyclic boron-containing π-ligands has remained relatively unexplored, presumably in part due to the higher reactivity of acyclic π-ligands relative to cyclic analogues. This perspective is focused on the synthesis, structures and reactivity of isolated transition metal complexes bearing η(n)-coordinated (n = 2 or 3) acyclic boron-containing ligands. Both monometallic and multimetallic compounds are included, and are discussed with an emphasis on metal-ligand and intraligand bonding and parallels with hydrocarbon π-ligand complexes.

Diversity of metal-ligand interactions in halide (X = I, Br, Cl, F) and halide-free ambiphilic ligand rhodium complexes.

Reaction of the neutral ambiphilic ligand 2,7-di-tert-butyl-5-diphenylboryl-4-diphenylphosphino-9,9-dimethylthioxanthene (TXPB) with [{Rh(mu-Cl)(CO)(2)}(2)] yields [RhCl(CO)(TXPB)] (1) (Emslie et al. Organometallics 2006, 25, 5835). Complex 1 is square planar with the TXPB ligand bound to rhodium via the phosphine and thioether donors (these are features common to complexes 2-5, vide infra). Treatment of 1 with Me(3)SiBr and Me(3)SiI allowed for halide substitution to afford [RhBr(CO)(TXPB)] (2) and [RhI(CO)(TXPB)] (3), respectively. The halide co-ligands in complexes 1 and 2 form a strong bridging interaction between rhodium and the borane group in TXPB. The presence of stronger borane-halide coordination in 1 is clearly illustrated by an (11)B NMR chemical shift of 12 ppm versus 27 ppm in 2. In contrast, the iodide ligand in 3 forms only a weak bridging interaction to boron, leading to a B...I distance of 3.125(7) A, and an (11)B NMR chemical shift of 56 ppm (versus 69 ppm for free TXPB). A lower carbonyl stretching frequency in 3 (2002 cm(-1)) versus 1 or 2 (2008 and 2013 cm(-1), respectively) could be attributed to weakening of the Rh-X bond in 1 and 2 as a consequence of halide-borane coordination and/or a shorter Rh-S bond in complex 3. [Rh(CO)(TXPB-F)] (4) and the halide-free cation [Rh(CO)(TXPB)][PF(6)] (5) were accessed by reaction of 1 with [NMe(4)]F and Tl[PF(6)], respectively. Complex 4 is zwitterionic with fluoride bound to boron [(11)B NMR delta 4 ppm; B-F = 1.445(6) A; Rh...F = 3.261(3) A] and an eta(2)-interaction between the cationic rhodium center and the ipso- and ortho-carbon atoms of a B-phenyl ring in TXPB-F. By contrast, rhodium in 5 engages in an eta(2)-interaction with boron and the ipso-carbon of one B-phenyl ring; Rh-B and Rh-C(ipso) bond lengths in 5 are 2.557(3) and 2.362(2) A, respectively. The long Rh-B distance and an (11)B NMR chemical shift of 57 ppm are consistent with only a weak Rh-B interaction in 5, and a CO stretching frequency of 2028 cm(-1) (Nujol), versus 2004-2013 cm(-1) for complexes 1-4, is indicative of greatly reduced electron density in 5, relative to 1-4.