Pentavalent lanthanide nitride-oxides: NPrO and NPrO⁻complexes with NPr triple bonds

Abstract

The neutral molecule NPrO and its anion NPrO– are characterized to be linear pentavalent praseodymium nitride-oxides that possess PrN triple bonds and PrO double bonds.

Triple Bonds Between Iron and Heavier Group 15 Elements in AFe(CO)3− (A=As, Sb, Bi) Complexes

“…Previously,only the AsCO À anion was experimentally reported, with the analogous SbCO À and BiCO À anions predicted to be stable. TheS bFe(CO) 3 À anion is further confirmed by isotopic splitting of antimony ( 121 Sb and 123 Sb). Thea ssignments are firmly established based on the isotopic splitting of iron along with the isotope-substituted experiments using the 13 CO sample (Supporting Information, Figure S1).…”

“…Dedicated to Professor Xintao Wu on the occasion of his 80th birthday Abstract: Heteronuclear transition-metal-main-group-element carbonyl complexes of AsFe(CO) 3 À ,S bFe(CO) 3 À ,a nd BiFe(CO) 3 À were produced by alaser vaporization supersonic ion source in the gas phase,and were studied by mass-selected IR photodissociation spectroscopya nd advanced quantum chemistry methods.T hese complexes have C 3v structures with all of the carbonyl ligands bonded on the iron center,a nd feature covalent triple bonds between bare Group 15 elements and Fe(CO) 3 À .Chemical bonding analyses on the whole series of AFe(CO) 3 À (A = N, P, As, S b, Bi, Mc) complexes indicate that the valence orbitals involved in the triple bonds are hybridized 3d and 4p atomic orbitals of iron, leading to an unusual (dp-p) type of transition-metal-main-group-element multiple bonding.The s-type three-orbital interaction between Fe 3d/4p and Group 15 np valence orbitals playsanimportant role in the bonding and stability of the heavier AFe(CO) 3 À (A = As,Sb, Bi)complexes.…”

“…[12] While triple bonding between transition metals and the heavier Group 14 and Group 15 elements is known, it is confined to the Group 5and Group 6 early transition metals. [16] Furthermore,aSbFe(CO) 3 À complex was generated in the gas phase in aF ourier transform ion cyclotron resonance spectrometer by reacting Sb 2 À with Fe(CO) 5 ,w hich has been postulated to have SbFe triple bonds based on formal 18-electron count. [16] Furthermore,aSbFe(CO) 3 À complex was generated in the gas phase in aF ourier transform ion cyclotron resonance spectrometer by reacting Sb 2 À with Fe(CO) 5 ,w hich has been postulated to have SbFe triple bonds based on formal 18-electron count.…”

“…[13] Af errogallyne was synthesized and characterized to involve Ga Fe triple bonds. [18] Herein we report the preparation of the AsFe(CO) 3 À ,S bFe(CO) 3 À ,a nd BiFe(CO) 3 À complexes in the gas phase.IRphotodissociation spectroscopy and advanced quantum chemistry studies confirm that all these species are triple bonded between bare heavier Group 15 elements and an Fe(CO) 3 À entity.T hese species can be explained via an intriguing three-orbital bonding model that involves substantial contribution of both Fe 3d and 4p orbitals in the bonding. [18] Herein we report the preparation of the AsFe(CO) 3 À ,S bFe(CO) 3 À ,a nd BiFe(CO) 3 À complexes in the gas phase.IRphotodissociation spectroscopy and advanced quantum chemistry studies confirm that all these species are triple bonded between bare heavier Group 15 elements and an Fe(CO) 3 À entity.T hese species can be explained via an intriguing three-orbital bonding model that involves substantial contribution of both Fe 3d and 4p orbitals in the bonding.…”

“…TheI Rp hotodissociation spectra of AFe( 12 CO) 3 À in the carbonyl stretching frequency region are shown in Figure 2, while the spectra for the 13 C-substituted AFe( 13 CO) 3 À anions are illustrated in the Supporting Information, Figure S2. The band positions are listed in Table 1.…”