Stability and stereochemistry of tetrahedral nickel nitrosyl complexes: crystal and molecular structures of (R*,S*)-anti-[NiNCS(NO){1,2-C6H4(PMePh)2}] and (R*,S*)-anti-[NiNO{P(OMe)3][1,2-C6H4(PMePh)2}]PF6

Abstract

solid P4S|0 and P4S9 and show that the major vapor components are molecular P4S10 and the terminal sulfur decomposition product P4S9.

Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO2)3][PF6]

“…In solution, 1 exhibits a high ν NO absorption feature in its IR spectrum (1877 cm –1 , CH 2 Cl 2 ). This ν NO value is higher than those observed for previously reported nickel nitrosyls (1568–1867 cm –1 ) ,− and can be attributed to the weak Lewis basicity of CH 3 NO 2 and its overall cationic charge . In contrast, this value is lower than that of [Cu(CH 3 NO 2 ) 5 (NO)][PF 6 ] 2 (1933 cm –1 , CH 3 NO 2 ) .…”

“…This is evidenced by large N–Ni–L angles (av. 127.9°), a feature common to many [Ni(NO)L 3 ] + and Ni(NO)L 2 X complexes. , The metrical parameters of the Ni–N–O moiety [Ni1–N1 = 1.626(6) Å; N1–O1 = 1.139(9) Å; Ni1–N1–O1 = 174.1(8)°; Table ] are within the range observed for other four-coordinate cationic {NiNO} 10 complexes. ,,− ,− Notably, the metrical parameters of the linear NO moiety in 1 are much different from those observed for the copper analogue [Cu(CH 3 NO 2 ) 5 (NO)][PF 6 ] 2 , which contains a much longer M–N bond and a bent nitrosyl ligand . Under the electron-counting rules normally used for linear nitrosyl ligands, complex 1 should be described with a Ni 0 –(NO + ) electronic structure.…”

Coordination and Organometallic Chemistry of Metal−NO Complexes

“…The related complex with L = 1,3,5-triaza-7-phosphaadamantane can be prepared in a similar manner . Also known are complexes of the type [Ni(NO)(L)(L−L)] + (L = a phosphine) and NiX(NO)(L−L) [X = Cl, Br, I, CN; L−L = 1,2-C 6 H 4 (PMePh) 2 ] . The related Ni(NO)(PPh 3 )(L) (L = 3,6-di- tert -butyl- o -benzosemiquinone) has been synthesized by reaction of TlL with Ni(NO)Br(PPh 3 ) 2 and has been characterized by ESR spectroscopy .…”

Three-Coordinate β-Diketiminato Nickel Nitrosyl Complexes from Nickel(I)−Lutidine and Nickel(II)−Alkyl Precursors

“…Examples characterized by X-ray are the pyrazolate-bridged nickel nitrosyls [(pz)Ni(NO)] 2 and [(pz) 2 Ni(NO)] 2 Ni (pz = 3,5-Me 2 N 2 C 3 H) 8 as well as the dinuclear iridium complex [Ir(NO)(PPh 3 )] 2 O . While most nickel nitrosyls are tetrahedral {MNO} complexes (following the classification of Enemark and Feltham) 10 of the types [Ni(NO)L 3 ] + ,, and [Ni(NO)XL 2 ] , (L = neutral donor; X = halogen or pseudo-halogen) that contain a linear nitrosyl ligand, the cylopentadienyl complexes Cp‘Ni(NO) − are probably the best studied Ni−NO species. Both CpNi(NO) 14 and Cp*Ni(NO) 16 have been shown to have a linear Ni−NO ground state, and a side-bound η 2 -NO photoexcited state has been characterized by X-ray crystallography for Cp*Ni(NO) .…”