Molecular orbital analysis of the metal–hydrazide(2−) bonding in co-ordination chemistry †

Bis(isodiazene) and related complexes of molybdenum(VI). Syntheses and structures of [Mo(OTf )2(NNPh2)2(py)2], [MoCl(OTf )(NNPh2){NC5H3(CH2C(O)Ph2)2-2,6}], [{MoCl(NNPh2)2(μ-Cl)(NH2But)}2] and [MoTp′Cl(NNPh2)2] [OTf = O3SCF3, Tp′ = tris(3,5-dimethylpyrazolyl)hydroborate]

“…DFT Calculations on isodiazene complexes have suggested an overall charge on the ligand closer to 1Ϫ than 2Ϫ, in accordance with the recently reported calculations of Carrillo and co-workers. 8 The bond lengths within the M-N-NR 2 systems were very similar to those observed previously with complexes of this type, and provide little direct information on formal metal oxidation state. Table 4 Selected bond lengths (Å) and angles (Њ) for compound 5…”

“…There are no notable intermolecular contacts. The structure of the related complex [MoTp(NNPh 2 ) 2 Cl] (Tp = hydrotris(pyrazolyl)borate) has been described, 8 and the bond lengths and angles are similar to those of 5.…”

Reaction Site Diversity in the Reactions of Titanium Hydrazides with Organic Nitriles, Isonitriles and Isocyanates: TiNα Cycloaddition, TiNα Insertion and NαNβ Bond Cleavage

“…We recently found that electron-deficient aryl groups (e.g., Ar = C 6 F 5 ) in metallacycles of the type 7 (Scheme 1) considerably stabilised these species relative to their analogues with Ar = Ph. We therefore hoped that using benzonitriles with fluorinated aryl groups, such as 2,6-C 6 (13) were formed in good isolated yields (and quantitatively when followed by 1 H NMR spectroscopy in C 6 D 6 ). In each instance, the pyridine ligand of 4 remained coordinated and the 1 H shift of the N 2 N py pyridyl hydrogen ortho to nitrogen was shifted significantly downfield, consistent with k 3 -N coordination of N 2 N py .…”

“…The Ti(1) À N(1) bond length of 2.3084(13) is significantly longer than the 2.1687(16) for Ti(1) À N(6) and is typical of N!Ti dative bonds in 5-coordinate systems. [13] Both of these Ti À N distances are much longer than Ti(1A)ÀN (6), which at 1.8684(14) is only about 0.1 longer than in 4 (Ti=N a = 1.759 (2) [5k]…”

Organometallic Compounds Containing the cis-[MoO(NNPhR)]2+ Core (R = Me, Ph) – X-ray Structures of [MoO(NNPh2)Me2(o-phen)] and [MoO(NNPh2)Ph2(o-phen)]

“…In both compounds, the molybdenum center displays distorted troscopy (see Experimental Section). [16,29] An extensive delocalization of the electron density throughout the Mo(NNPh 2 ) units is supported by (i) the short MoϪN (3) (2) and 1.711(4) Å in 5 and 7, respectively, fall within the normal range [29] and, in line with expectation, [15] the trans influence exerted by this group is clearly far more important than that exerted by the (2) coordination chemistry, [16] if formally considered as a diand C(61)ϪMoϪN(2) bond angles are 76.7(2) and 78.6(2)°a nion, the hydrazido ligand represents a six-electron donor while the C(51)ϪMoϪN(1) and C(61)ϪMoϪN(1) bond when it is coordinated in a linear mode in monohydrazido angles are 89.5(2) and 81.5(2)°. The spectrum of complex 2 contain-equatorial plane being defined by the oxo group, the N (1) and N(2) atoms of the o-phenanthroline, and the N(3) atom ing the NNMePh ligand, which had to be recorded in [D 6 ]DMSO solution owing to the low solubility of this of the organohydrazido ligand.…”