Nitrosyl hydride

Bazylinski, D. A., and Hollocher, T. C. (1985b). Metmyoglobin and methemoglobin as efficient traps for nitrosyl hydride (nitroxyl) in neutral aqueous solution. J. Am. Chem. Soc. 107, 7982-7986. 

Bonner, F. T., and Pearsall, K. A. (1982). Aqueous nitrosyliron(ll) chemistry. 1. Reduction of nitrite and nitric oxide by iron(ll) and (trioxodinitrato)iron(ll) in acetate buffer. Intermediacy of nitrosyl hydride. Inorg. Chem. 21, 1973-1978. 

Cp and poly(pyrazolyl)borates also stabilize polyhydrides, for example, ReCpH4(PR3) and ReH4 ic -HB(OR)(3,5-Me2pz)2 (PPh3). Nitrosyl hydrides, ReH4 (NO)3,E4, are mentioned in Section 13. 

NO induces a strong hydridic polarization of the Re-H bond in nitrosyl hydrides, the nitrosyl effect . The conjugation of these properties enables them to perform the heterolytic cleavage of H2 and RsSi-H bonds as depicted in Scheme 35 as well as the insertion of Re-H bonds into polar unsaturated organic substrates. ... 

Nitrosyl complexes are rather numerous and [Re(NO)Xs] is known for all the halides (= X) addition of phen or bipy (= L-L) gives [Re(NO)X3(L-L)] or of pyridine, alcohols, DMSO, or MeCN (= solv) gives [Re(NO)X4(solv)] PPhs in EtOH followed by NaBH4 gives the nitrosyl hydride [ReH2(NO)(PPh3)3]. Other nitrosyl complexes include [Re(NO)Cl2(OMe)(PPh3)2] and [Tc(NO)Br4] and the low-valent complexes indicated above. 

The preparation of compounds containing nitrogen double bonded to another heteroatom has been accomplished by a rDA pathway. Cis- and (rnns-azomethane have been synthesized from tetrahydropyrida-zine (171) by thermal retrodiene extrusion (equation 77). The anti conformation of (171) is presumed to give (rnns-azomethane and the syn conformations yields the cis-isomer. Preparation of nitrosyl hydride (173) has been accomplished under mild nonphotochemical conditions, unlike conditions used in previous preparations. The extrusion of nitrosyl hydride from anthracene adduct (172) as shown in equation (78), which occurs at a very mild temperature, was followed by microwave detection of (173). 

Niobiun bronlde (NbBrg) BT3Nb (cr) 524 - / Nitrosyl hydride (HNO) Hj NjOj(g) 1237... 

SCF calculations have been carried out on the molecule HNO ( nitrosyl hydride ) and its isomer HON ( nitrogen hydroxide ). " The system is found to have a low-lying triplet state, which is expected to aid in the dimerization to hyponitrous acid, H2O2N2. 

The first and only nitrosyl hydride has been prepared recently by the reduction of the complex MnBr(NO)2(PPh3)2 with sodium boro-hydride (170). It may be noted that reduction of the nitrosylcarbonyl (ir-C5H5)Cr(CO)(NO)Br does not give a Cr—H complex. A possible polynuclear technetium hydride [Tc(CO)4]3H has been discussed (186). Reduction of the complex CH3SCH2CH2SCH3Mo(CO)3l2 affords an unstable hydride (215). 

Nitrosyl hydride HO-N 98.1 410.4 Derived from AfJT in ref. 1996NIST... 

First, we look at the term which is closely related to the term from the perturbational analysis. The trend predicted for the influence of the trans-ligand is reflected in the values. We also note that the orbital interaction energy for the tungsten nitrosyl hydride systems is essentially the same, independent of the number of phosphine ligands. For all three compounds, the steric contribution AP is stabilizing, and therefore dominated by attractive electrostatic interactions. Increasing the number of P-donors further increases the absolute value of A , and strengthens the TM-H bond. 

In our group we have applied all three methods to study dihydrogen bonding of transition metal nitrosyl hydrides [25-27] These studies led to an overall consistent picture of the general phenomenon of dihydrogen bonding, and of the basic character of transition metal hydrides. 

As mentioned before, we have studied in our group various types of insertion reactions with phosphine substituted transition metal nitrosyl hydrides [37]. In general, these compounds appear to have a very hydridic bond, but also... 

We suggest that the initial step is heterolytic splitting of H2 or Dj, leading to the protonated or deuterated transition metal nitrosyl hydrides or deuterides, respectively. H/D exchange via the second nitrosyl ligand might lead to the mixed hydride-deuteride complex, which in a reverse reaction forms HD, and regenerates the cationic catalyst. 

A. Messmer Rhenium-Nitrosyl-Hydride mit aktivierten Metall-WasserstofF-bindungen. Dissertation University of Zurich, 1999, Hartung-Gorre, Konstanz, 2000. 

---