doi:10.1016/j.cplett.2004.11.066 
Copyright © 2004 Elsevier B.V. All rights reserved.
Spin-philicity and spin-donicity of simple nitrenes and phosphinidenes
aDepartment of Inorganic Chemistry, Budapest University of Technology and Economics, S. Gellért tér 4, H-1521 Budapest, Hungary
bDepartment of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
Received 6 August 2004;
revised 15 November 2004.
Available online 9 December 2004.
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Abstract
Spin indices of some simple nitrenes (R-N) and phosphinidenes (R-P), in both lowest-lying singlet and triplet states, have been evaluated using density functional computations at the B3LYP/6-311+G(d,p) level. Relatively good correlations between the spin hardness, spin-philicity and spin-donicity, and the vertical singlet–triplet energy gaps have been established. A comparison with spin indices of related reactive intermediates such as carbenes, silylenes and germylenes allows their similarities and differences to be emphasized.
Fig. 1. Spin-donicity index (in eV) vs. the vertical singlet–triplet gap (in kcal/mol) for nitrenes (
) and phosphinidenes (■).
Fig. 2. Maximal spin release (
) (in spins) vs. the vertical singlet–triplet gap (in kcal/mol) for nitrenes () and phosphinidenes (■).
Fig. 3. (a) Spin hardness of nitrenes plotted against the spin hardness of phosphinidenes. (b) Spin hardness of nitrenes plotted against the spin hardness of triplet carbenes.
Table 1.
Adiabatic singlet–triplet gap, vertical singlet–triplet gap, spin-related DFT descriptors (spin potential (μ−), spin hardness 
, spin-donicity 
and maximal spin acceptance 
for the nitrenes and the phosphinidenesa
a Adiabatic singlet–triplet energy separation and vertical energies in kcal/mol, spin potential values in volts, spin-hardness in volt/spin units, spin-philicity and spin-donicity values in eV, maximal spin acceptance in spins.
b The compound rearranged to the double-bonded species on the singlet potential energy surface we did not calculate the ‘adiabatic’ singlet–triplet gap.
Table 2.
R2 values for the linear regression between the spin hardness values of carbenes, silylenes, germylenes, nitrenes and phospinidenes (values given in brackets refer to the triplet state of carbenes, silylenes and germylenes)
Table 3.
R2 values for the linear regression between the spin-philicity of carbenes, silylenes, germylenes and spin-donicity values of nitrenes and phospinidenes (values given in brackets refer to the triplet state i.e. the spin-donicity index of carbenes, silylenes and germylenes)
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