Dinitrogen binding and electrochemistry in complexes of molybdenum and tungsten

Exploring the role of pendant amines in transition metal complexes for the reduction of N2 to hydrazine and ammonia

“…Cyclic voltammetry experiments were performed on these Mo−N2 complexes and the results are summarized in Table 1. As expected, the half-wave potentials of Mo I/0 couple are in accordance with the electron-donating ability of the substituents on the phosphorous atoms [70]. CH2CH2NMe2 21; CH2-o-Py (22)) were prepared to examine their reactivity with acid [71].…”

Infrared spectroscopic studies of transition metal complexes and polarizability effect

“…As is known, the different P properties of the TMC are related to each other by the linear dependences. These are observed (for the individual series or for the structurally related compounds) between k(CS) and k(CO), k(CS) and 13 C NMR thiocarbonyl chemical shifts d(CS), d(CS) and d(CO) [9], n(CS) and k(CO) [45]; n(CN) and inductive constants s * , n(CN) and pK b values of nitrogen-donor bases B for the (B)Co (CN)(DH) 2 (DH ¼ dimethylglyoxime) complexes [6]; n(CN) and phosphine basicity for the (X 3 P) 2 Ru(CN)(h 5 -C 5 H 5 ) complexes, n(CN) and cyanide basicity for the (X 3 P) 2 RuCN(Cp 0 ) (Cp 0 ¼ h 5 -C 5 H 5 or h 5 -C 5 Me 5 ) complexes [18]; n(NC) and n(CO), n(NC) and Hammett parameters s for selected complexes, n(NC) and the relative strengths of the Nieolefin bonds in the complexes (olefin)Ni (t-BuNC) 2 [8], k(NC) and orbital occupations [50]; n(NN) and Hammett parameters s p [50], n(NN) and parameters s p þ [54], k(NN) and half-wave potentials E 1/2 (ox) [15]; n(NO) and log K eq for the reaction: (cat)Ir(NO)(PPh 3 ) þ PPh 3 5 (cat)Ir(NO)(PPh 3 ) 2 (cat ¼ catecholato) [10], n(NO) and E 1/2 (ox) [15,55] as well as n(NO) and n(CO). For example, the equations n(NO) ¼ À(259 AE 234) þ (1.01 AE 0.11)n(CO) (S Y ¼ 3, R ¼ 0.981, n ¼ 5) and n (NO) ¼ À(218 AE 57) þ (0.99 AE 0.03)n(CO) (S Y ¼ 1, R ¼ 0.998, n ¼ 7) are valid for series XXI and XXII, respectively.…”

Structural diversity of tetranuclear tungsten sulfide clusters: syntheses and crystal structures of clusters containing raft-type W4(μ3-S)2(μ-S)4 and tetrahedral W4(μ-S)6 cores

“…[W 4 ( 3 -S) 2 ( -S) 4 (SH) 2 (PMe 2 Ph) 6 ] 2. To a toluene solution (60 cm 3 ) of cis-[W(N 2 ) 2 (PMe 2 Ph) 4 ] 1 11 (3.013 g, 3.80 mmol) in a two-necked round-bottomed flask (500 cm 3 ) was added MeOH (1.5 cm 3 , 37 mmol), and the solution was allowed to cool to Ϫ196 ЊC. Then (Me 3 Si) 2 S (1.6 cm 3 , 7.6 mmol) was added at this temperature and the flask evacuated after all the materials inside had frozen.…”