Two derivatives of a new bis(pyrazolyl)carbazole pincer ligand H(CzPz R ), R = i Pr and Me, and their syntheses are reported. Lutetium dialkyl complexes of the ligand (CzPz R )Lu(CH 2 SiMe 3 ) 2 , R = i Pr and Me, have been prepared and found to exhibit high thermal stability in solution. These organolutetium compounds are Lewis base free, and the solid-state structure of (CzPz iPr )Lu(CH 2 SiMe 3 ) 2 revealed that the complex is monomeric with a trigonalbipyramidal geometry. Hydrogenolysis of (CzPz iPr )Lu(CH 2 SiMe 3 ) 2 afforded a trimetallic lutetium hydride complex that possesses five bridging hydride ligands. Notably, intramolecular C−H bond activation of the CzPz iPr ligand was found to occur during the formation of this latter hydride complex, with metalation of a pyrazole carbon atom.

M06-2X/6-31G(d,p) is used to calculate the structure of all natural deoxydinucleoside monophosphates with G in the 5' or 3' position, the anti or syn conformation, and each natural (A, C, G, T) base in the corresponding flanking position. When the ortho or para C8-phenoxyl-2'-deoxyguanosine (C8-phenoxyl-dG) adduct replaces G in each model, there is little change in the relative base-base orientation or backbone conformation. However, the orientation of the C8-phenoxyl group can be characterized according to the position (5' versus 3'), conformation (anti versus syn), and isomer (ortho versus para) of damage. Although the degree of coplanarity between the phenoxyl ring and G base in the ortho adduct is highly affected by the sequence since the hydroxyl group can interact with neighboring bases, the para adduct generally does not exhibit discrete interactions with flanking bases. For both adducts, steric clashes between the phenoxyl group and the backbone or flanking base destabilize the anti conformation preferred by the natural nucleotide and thereby result in a clear preference for the syn conformation regardless of the sequence or position. This contrasts the conclusions drawn from smaller (nucleoside, nucleotide) models previously used in the literature, which stresses the importance of using models that address the steric constraints present due to the surrounding environment. Since replication errors for other C8-dG bulky adducts have been linked to a preference for the syn conformation, our findings provide insight into the possible mutagenicity of phenolic adducts.

The synthesis and reactivity of two new bis(phosphinimine)carbazole ligands (PippN=PMe2)2DMC (HLA, 3) and (PippN=P(C4H8))2DMC (HLB, 10), where Pipp = para-isopropylphenyl and DMC = 3,6-dimethylcarbazole, are reported. Dialkyl lutetium complexes of 3 and 10 were prepared in the presence of DMAP and THF by reaction of the proteo ligands with the new trialkyl reagent, Lu(CH2SiMe3)3(DMAP)2 (4) as well as Lu(CH2SiMe3)3(THF)2. For both ligands 3 and 10, the resulting lutetium complexes were prone to intramolecular cyclometalative alkane elimination reactions whereby the location of cyclometalation was influenced by the identity of the ancillary ligand coordinated to the metal. For ligand 3, cyclometalation of two PMe2 groups generated the complex (LA-κ3N,κ2C)Lu(DMAP)2 (5), whereas ligand 10 resulted in the single ortho-metalation of a para-isopropylphenyl ring to afford (LB-κ3N,κC)Lu(CH2SiMe3) (12). When complexed with scandium, ligand 10 behaved differently; double cyclometalation of two phospholane moieties resulted in the species (LB-κ3N,κ2C)Sc (15). The nature of the cyclometalation reactivity of ligands 3 and 10 is supported by X-ray crystallography and kinetic analysis, respectively.