Chiral Heterobimetallic Bismuth-Rhodium Paddlewheel Catalysts: A Conceptually New Approach to Asymmetric Cyclopropanation.

Cyclopropanation reactions of styrene derivatives with donor-acceptor carbenes formed in situ are significantly more enantioselective when catalyzed by the heterobimetallic bismuth-rhodium complex 5 a endowed with N-phthalimido tert-leucine paddlewheel ligands rather than by its homobimetallic dirhodium analogue 1 a. This virtue is likely the result of two synergizing factors: the conical shape of 5 a translates into a narrower calyx-like chiral binding site about the catalytically active Rh center; the Bi atom, although fully solvent exposed, does not decompose aryl diazoacetates and is hence incapable of promoting a racemic background reaction. Moreover, ligand variation proved that successful catalyst design mandates that the anisotropy of the conical heterobimetallic core be matched by proper directionality of the ligand sphere.

Enhanced Electrophilicity of Heterobimetallic Bi-Rh Paddlewheel Carbene Complexes: A Combined Experimental, Spectroscopic, and Computational Study.

Dirhodium paddlewheel complexes are indispensable tools in modern organometallic catalysis for the controlled decomposition of diazo-compounds. Tuning the reactivity of the thus-formed transient carbenes remains an active and dynamic field of research. Herein, we present our findings that the distal metal center plays an as yet underappreciated role in modulating this reactivity.

Synthesis and characterization of phosphorescent two-coordinate copper(i) complexes bearing diamidocarbene ligands.

The photophysical properties of four, two-coordinate, linear diamidocarbene copper(i) complexes, [(DAC)Cu][BF] (1), (DAC)CuOSiPh (2), (DAC)CuCF (3) and (DAC)Cu(2,4,6-MeCH) (4) (DAC = 1,3-bis(2,4,6-trimethylphenyl)-5,5-dimethyl-4,6-diketopyrimidinyl-2-ylidene) have been investigated. Complex 1 shows a high photoluminescence quantum efficiency (Φ) in both the solid state (Φ = 0.85) and in CHCl solution (Φ = 0.

Experimental and Computational Studies of the Copper Borate Complexes [(NHC)Cu(HBEt )] and [(NHC)Cu(HB(C F ) )].

The synthesis of the Cu-borate complexes [(6Mes)Cu(HBR )] featuring the unusual [HBEt ] (5) and [HB(C F ) ] (6) ligands is described. Experimental and computational studies show both compounds feature a direct Cu-H interaction, but that while 5 is two-coordinate, 6 displays an additional, stabilizing Cu-C (C F ) interaction.

A Comparison of the Stability and Reactivity of Diamido- and Diaminocarbene Copper Alkoxide and Hydride Complexes.

The mononuclear N-heterocyclic carbene (NHC) copper alkoxide complexes [(6-NHC)CuOtBu] (6-NHC = 6-MesDAC (1), 6-Mes (2)) have been prepared by addition of the free carbenes to the tetrameric tert-butoxide precursor [Cu(OtBu)]4, or by protonolysis of [(6-NHC)CuMes] (6-NHC = 6-MesDAC (3), 6-Mes (4)) with tBuOH. In contrast to the relatively stable diaminocarbene complex 2, the diamidocarbene derivative 1 proved susceptible to both thermal and hydrolytic ring-opening reactions, the latter affording [(6-MesDAC)Cu(OC(O)CMe2C(O)N(H)Mes)(CNMes)] (6). The intermediacy of [(6-MesDAC)Cu(OH)] in this reaction was supported by the generation of Cu2O as an additional product.

Unexpected migratory insertion reactions of M(alkyl)2 (M=Zn, Cd) and diamidocarbenes.

The electrophilic character of free diamidocarbenes (DACs) allows them to activate inert bonds in small molecules, such as NH3 and P4 . Herein, we report that metal coordinated DACs also exhibit electrophilic reactivity, undergoing attack by Zn and Cd dialkyl precursors to afford the migratory insertion products [(6-MesDAC-R)MR] (M=Zn, Cd; R=Et, Me; Mes=mesityl). These species were formed via the spectroscopically characterised intermediates [(6-MesDAC)MR2 ], exhibiting barriers to migratory insertion which increase in the order MR2 = ZnEt2 < ZnMe2 < CdMe2 .

Copper diamidocarbene complexes: characterization of monomeric to tetrameric species.

Treatment of CuCl with 1 equiv of the in situ prepared N-mesityl-substituted diamidocarbene 6-MesDAC produced a mixture of the dimeric and trimeric copper complexes [(6-MesDAC)CuCl]2 (1) and [(6-MesDAC)2(CuCl)3] (2). Combining CuCl with isolated, free 6-MesDAC in 1:1 and 3:2 ratios gave just 1 and 2, respectively, while increasing the ratio to >5:1 allowed the isolation of small amounts of the tetrameric copper complex [(6-MesDAC)2(CuCl)4] (3). Efforts to bring about metathesis reactions of 1 with MO(t)Bu (M = Li, Na, K) proved successful only for M = Li to afford the spectroscopically characterized ate product [(6-MesDAC)CuCl·LiO(t)Bu·2THF] (5).

RESOLVE and access to care: the patient response to anti-family policies.

RESOLVE: The National Infertility Association was founded in 1974 to provide support and information for women and men living with infertility. RESOLVE has worked to increase access to care beginning with insurance coverage for infertility and more recently in fighting anti-family legislation in many state legislatures. Beginning with the Personhood ballot initiative in Colorado in 2008, RESOLVE and its grassroots advocates have been called into action to fight legislative attempts to restrict access to all family-building options, specifically in vitro fertilization.

Fighting 'personhood' initiatives in the United States.

'Personhood' initiatives filed in many states within the United States threaten to impose potentially significant restrictions on infertility treatment, embryo disposition, pre-natal care, abortion, contraception, and stem-cell research, all through attempts to redefine a 'person' or 'human being' as existing from the moment of fertilization or conception, and endowed with the full legal and Constitutional rights of personhood. Virginia's recent, unsuccessful attempt to pass such legislation provides both a dramatic example of these efforts and valuable lessons in the fight against them by infertility advocates and others. Arguments over loss of infertility treatment seemed more persuasive to legislatures than did restrictions on abortion or stem cell research.