Linear correlation between effective charge and bond length sensitivity to electronic effects in phosphoryl, sulfonyl, and sulfuryl compounds

2013 ◽  
Vol 27 (4) ◽  
pp. 358-366 ◽  
Author(s):  
Tiago A. S. Brandão
Keyword(s):  
Bond Length ◽  
Linear Correlation ◽  
Effective Charge ◽  
Electronic Effects

scholarly journals Complex transition metal hydrides: linear correlation of countercation electronegativity versus T–D bond lengths

2015 ◽  
Vol 51 (56) ◽  
pp. 11248-11251 ◽  
Author(s):  
T. D. Humphries ◽  
D. A. Sheppard ◽  
C. E. Buckley
Keyword(s):  
Transition Metal ◽  
Bond Length ◽  
Linear Correlation ◽  
Metal Hydrides ◽  
Bond Lengths ◽  
Transition Metal Hydrides ◽  
Complex Hydrides

For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T–deuterium bond length and the average electronegativity of the metal countercations.

scholarly journals Bond-Length Distributions for Ions Bonded to Oxygen: Results for the Transition Metals and Quantification of the Factors Underlying Bond-Length Variation in Inorganic Solids

2020 ◽  
Author(s):  
Olivier Charles Gagné ◽  
Frank Christopher Hawthorne
Keyword(s):  
Transition Metal ◽  
Bond Length ◽  
A Priori ◽  
Bond Formation ◽  
Length Variation ◽  
Electronic Effects ◽  
Coordination Polyhedra ◽  
Jahn Teller ◽  
Jahn Teller Effect ◽  
Non Local

Bond-length distributions are examined for 63 transition-metal ions bonded to O2- in 147 configurations, for 7522 coordination polyhedra and 41,488 bond distances, providing baseline statistical knowledge of bond lengths for transi-tion metals bonded to O2-. A priori bond valences are calculated for 140 crystal structures containing 266 coordination poly-hedra for 85 transition-metal ion configurations with anomalous bond-length distributions. Two new indices, Δ𝑡𝑜𝑝𝑜𝑙 and Δ𝑐𝑟𝑦𝑠𝑡, are proposed to quantify bond-length variation arising from bond-topological and crystallographic effects in extended solids. Bond-topological mechanisms of bond-length variation are [1] non-local bond-topological asymmetry, and [2] multi-ple-bond formation; crystallographic mechanisms are [3] electronic effects (with inherent focus on coupled electronic-vibra-tional degeneracy in this work), and [4] crystal-structure effects. The Δ𝑡𝑜𝑝𝑜𝑙 and Δ𝑐𝑟𝑦𝑠𝑡 indices allow one to determine the primary cause(s) of bond-length variation for individual coordination polyhedra and ion configurations, quantify the dis-torting power of cations via electronic effects (by subtracting the bond-topological contribution to bond-length variation), set expectation limits regarding the extent to which functional properties linked to bond-length variations may be optimized in a given crystal structure (and inform how optimization may be achieved), and more. We find the observation of multiple bonds to be primarily driven by the bond-topological requirements of crystal structures in solids. However, we sometimes observe multiple bonds to form as a result of electronic effects (e.g. the pseudo Jahn-Teller effect); resolution of the origins of multiple-bond formation follows calculation of the Δ𝑡𝑜𝑝𝑜𝑙 and Δ𝑐𝑟𝑦𝑠𝑡 indices on a structure-by-structure basis. Non-local bond-topological asymmetry is the most common cause of bond-length variation in transition-metal oxides and oxysalts, followed closely by the pseudo Jahn-Teller effect (PJTE). Non-local bond-topological asymmetry is further suggested to be the most widespread cause of bond-length variation in the solid state, with no a priori limitations with regard to ion identity. Overall, bond-length variations resulting from the PJTE are slightly larger than those resulting from non-local bond-topological asym-metry, comparable to those resulting from the strong JTE, and less than those induced by π-bond formation. From a compar-ison of a priori and observed bond valences for ~150 coordination polyhedra in which the strong JTE or the PJTE is the main reason underlying bond-length variation, the Jahn-Teller effect is found not to have a symbiotic relation with the bond-topo-logical requirements of crystal structures. The magnitude of bond-length variations caused by the PJTE decreases in the fol-lowing order for octahedrally coordinated d0 transition metals oxyanions: Os8+ > Mo6+ > W6+ >> V5+ > Nb5+ > Ti4+ > Ta5+ > Hf4+ > Zr4+ > Re7+ >> Y3+ > Sc3+. Such ranking varies by coordination number; for [4], it is Re7+ > Ti4+ > V5+ > W6+ > Mo6+ > Cr6+ > Os8+ >> Mn7+; for [5], it is Os8+ > Re7+ > Mo6+ > Ti4+ > W6+ > V5+ > Nb5+. We conclude that non-octahedral coordinations of d0 ion configurations are likely to occur with bond-length variations that are similar in magnitude to their octahedral counterparts. However, smaller bond-length variations are expected from the PJTE for non-d0 transition-metal oxyanions.<br>

scholarly journals The Ultrafast Photoisomerizations of Rhodopsin and Bathorhodopsin Are Modulated by Bond Length Alternation and HOOP Driven Electronic Effects

2011 ◽  
Vol 133 (10) ◽  
pp. 3354-3364 ◽  
Author(s):  
Igor Schapiro ◽  
Mikhail Nikolaevich Ryazantsev ◽  
Luis Manuel Frutos ◽  
Nicolas Ferré ◽  
Roland Lindh ◽  
...  
Keyword(s):  
Bond Length ◽  
Electronic Effects ◽  
Bond Length Alternation

Enthalpies of Reaction of (.eta.5-C5H5)Ru(cyclooctadiene)Cl with Tertiary Phosphine Ligands: Ligand Substitution as a Gauge for Metal Basicity and A Linear Correlation of Bond Length and Bond Enthalpy

1995 ◽  
Vol 14 (1) ◽  
pp. 289-296 ◽  
Author(s):  
Michele E. Cucullu ◽  
Lubin Luo ◽  
Steven P. Nolan ◽  
Paul J. Fagan ◽  
Nancy L. Jones ◽  
...  
Keyword(s):  
Bond Length ◽  
Linear Correlation ◽  
Ligand Substitution ◽  
Phosphine Ligands ◽  
Tertiary Phosphine

scholarly journals Bond-Length Distributions for Ions Bonded to Oxygen: Results for the Transition Metals and Quantification of the Factors Underlying Bond-Length Variation in Inorganic Solids

2020 ◽  
Author(s):  
Olivier Charles Gagné ◽  
Frank Christopher Hawthorne
Keyword(s):  
Transition Metal ◽  
Bond Length ◽  
A Priori ◽  
Bond Formation ◽  
Length Variation ◽  
Electronic Effects ◽  
Coordination Polyhedra ◽  
Jahn Teller ◽  
Jahn Teller Effect ◽  
Non Local

Bond-length distributions are examined for 63 transition-metal ions bonded to O2- in 147 configurations, for 7522 coordination polyhedra and 41,488 bond distances, providing baseline statistical knowledge of bond lengths for transi-tion metals bonded to O2-. A priori bond valences are calculated for 140 crystal structures containing 266 coordination poly-hedra for 85 transition-metal ion configurations with anomalous bond-length distributions. Two new indices, Δ𝑡𝑜𝑝𝑜𝑙 and Δ𝑐𝑟𝑦𝑠𝑡, are proposed to quantify bond-length variation arising from bond-topological and crystallographic effects in extended solids. Bond-topological mechanisms of bond-length variation are [1] non-local bond-topological asymmetry, and [2] multi-ple-bond formation; crystallographic mechanisms are [3] electronic effects (with inherent focus on coupled electronic-vibra-tional degeneracy in this work), and [4] crystal-structure effects. The Δ𝑡𝑜𝑝𝑜𝑙 and Δ𝑐𝑟𝑦𝑠𝑡 indices allow one to determine the primary cause(s) of bond-length variation for individual coordination polyhedra and ion configurations, quantify the dis-torting power of cations via electronic effects (by subtracting the bond-topological contribution to bond-length variation), set expectation limits regarding the extent to which functional properties linked to bond-length variations may be optimized in a given crystal structure (and inform how optimization may be achieved), and more. We find the observation of multiple bonds to be primarily driven by the bond-topological requirements of crystal structures in solids. However, we sometimes observe multiple bonds to form as a result of electronic effects (e.g. the pseudo Jahn-Teller effect); resolution of the origins of multiple-bond formation follows calculation of the Δ𝑡𝑜𝑝𝑜𝑙 and Δ𝑐𝑟𝑦𝑠𝑡 indices on a structure-by-structure basis. Non-local bond-topological asymmetry is the most common cause of bond-length variation in transition-metal oxides and oxysalts, followed closely by the pseudo Jahn-Teller effect (PJTE). Non-local bond-topological asymmetry is further suggested to be the most widespread cause of bond-length variation in the solid state, with no a priori limitations with regard to ion identity. Overall, bond-length variations resulting from the PJTE are slightly larger than those resulting from non-local bond-topological asym-metry, comparable to those resulting from the strong JTE, and less than those induced by π-bond formation. From a compar-ison of a priori and observed bond valences for ~150 coordination polyhedra in which the strong JTE or the PJTE is the main reason underlying bond-length variation, the Jahn-Teller effect is found not to have a symbiotic relation with the bond-topo-logical requirements of crystal structures. The magnitude of bond-length variations caused by the PJTE decreases in the fol-lowing order for octahedrally coordinated d0 transition metals oxyanions: Os8+ > Mo6+ > W6+ >> V5+ > Nb5+ > Ti4+ > Ta5+ > Hf4+ > Zr4+ > Re7+ >> Y3+ > Sc3+. Such ranking varies by coordination number; for [4], it is Re7+ > Ti4+ > V5+ > W6+ > Mo6+ > Cr6+ > Os8+ >> Mn7+; for [5], it is Os8+ > Re7+ > Mo6+ > Ti4+ > W6+ > V5+ > Nb5+. We conclude that non-octahedral coordinations of d0 ion configurations are likely to occur with bond-length variations that are similar in magnitude to their octahedral counterparts. However, smaller bond-length variations are expected from the PJTE for non-d0 transition-metal oxyanions.<br>

Bond-length distributions for ions bonded to oxygen: results for the lanthanides and actinides and discussion of the f-block contraction

2018 ◽  
Vol 74 (1) ◽  
pp. 49-62 ◽  
Author(s):  
Olivier Charles Gagné
Keyword(s):  
Bond Length ◽  
Coordination Number ◽  
Crystal Chemistry ◽  
Linear Correlation ◽  
Lanthanide Ions ◽  
Coordination Polyhedra ◽  
Trivalent Lanthanides ◽  
Lanthanide Contraction ◽  
Trivalent Lanthanide ◽  
Actinide Ions

Bond-length distributions have been examined for 84 configurations of the lanthanide ions and 22 configurations of the actinide ions bonded to oxygen, for 1317 coordination polyhedra and 10 700 bond distances for the lanthanide ions, and 671 coordination polyhedra and 4754 bond distances for the actinide ions. A linear correlation between mean bond length and coordination number is observed for the trivalent lanthanides ions bonded to O2−. The lanthanide contraction for the trivalent lanthanide ions bonded to O2− is shown to vary as a function of coordination number, and to diminish in scale with an increasing coordination number. The decrease in mean bond length from La3+ to Lu3+ is 0.25 Å for coordination number (CN) 6 (9.8%), 0.22 Å for CN 7 (8.7%), 0.21 Å for CN 8 (8.0%), 0.21 Å for CN 9 (8.2%) and 0.18 Å for CN 10 (6.9%). The crystal chemistry of Np5+ and Np6+ is shown to be very similar to that of U6+ when bonded to O2−, but differs for Np7+.

scholarly journals Bond-Length Distributions for Ions Bonded to Oxygen: Results for the Transition Metals and Quantification of the Factors Underlying Bond-Length Variation in Inorganic Solids

2020 ◽  
Author(s):  
Olivier Charles Gagné ◽  
Frank Christopher Hawthorne
Keyword(s):  
Transition Metal ◽  
Bond Length ◽  
A Priori ◽  
Bond Formation ◽  
Length Variation ◽  
Electronic Effects ◽  
Coordination Polyhedra ◽  
Jahn Teller ◽  
Jahn Teller Effect ◽  
Non Local

Bond-length distributions are examined for 63 transition-metal ions bonded to O2- in 147 configurations, for 7522 coordination polyhedra and 41,488 bond distances, providing baseline statistical knowledge of bond lengths for transi-tion metals bonded to O2-. A priori bond valences are calculated for 140 crystal structures containing 266 coordination poly-hedra for 85 transition-metal ion configurations with anomalous bond-length distributions. Two new indices, Δ𝑡𝑜𝑝𝑜𝑙 and Δ𝑐𝑟𝑦𝑠𝑡, are proposed to quantify bond-length variation arising from bond-topological and crystallographic effects in extended solids. Bond-topological mechanisms of bond-length variation are [1] non-local bond-topological asymmetry, and [2] multi-ple-bond formation; crystallographic mechanisms are [3] electronic effects (with inherent focus on coupled electronic-vibra-tional degeneracy in this work), and [4] crystal-structure effects. The Δ𝑡𝑜𝑝𝑜𝑙 and Δ𝑐𝑟𝑦𝑠𝑡 indices allow one to determine the primary cause(s) of bond-length variation for individual coordination polyhedra and ion configurations, quantify the dis-torting power of cations via electronic effects (by subtracting the bond-topological contribution to bond-length variation), set expectation limits regarding the extent to which functional properties linked to bond-length variations may be optimized in a given crystal structure (and inform how optimization may be achieved), and more. We find the observation of multiple bonds to be primarily driven by the bond-topological requirements of crystal structures in solids. However, we sometimes observe multiple bonds to form as a result of electronic effects (e.g. the pseudo Jahn-Teller effect); resolution of the origins of multiple-bond formation follows calculation of the Δ𝑡𝑜𝑝𝑜𝑙 and Δ𝑐𝑟𝑦𝑠𝑡 indices on a structure-by-structure basis. Non-local bond-topological asymmetry is the most common cause of bond-length variation in transition-metal oxides and oxysalts, followed closely by the pseudo Jahn-Teller effect (PJTE). Non-local bond-topological asymmetry is further suggested to be the most widespread cause of bond-length variation in the solid state, with no a priori limitations with regard to ion identity. Overall, bond-length variations resulting from the PJTE are slightly larger than those resulting from non-local bond-topological asym-metry, comparable to those resulting from the strong JTE, and less than those induced by π-bond formation. From a compar-ison of a priori and observed bond valences for ~150 coordination polyhedra in which the strong JTE or the PJTE is the main reason underlying bond-length variation, the Jahn-Teller effect is found not to have a symbiotic relation with the bond-topo-logical requirements of crystal structures. The magnitude of bond-length variations caused by the PJTE decreases in the fol-lowing order for octahedrally coordinated d0 transition metals oxyanions: Os8+ > Mo6+ > W6+ >> V5+ > Nb5+ > Ti4+ > Ta5+ > Hf4+ > Zr4+ > Re7+ >> Y3+ > Sc3+. Such ranking varies by coordination number; for [4], it is Re7+ > Ti4+ > V5+ > W6+ > Mo6+ > Cr6+ > Os8+ >> Mn7+; for [5], it is Os8+ > Re7+ > Mo6+ > Ti4+ > W6+ > V5+ > Nb5+. We conclude that non-octahedral coordinations of d0 ion configurations are likely to occur with bond-length variations that are similar in magnitude to their octahedral counterparts. However, smaller bond-length variations are expected from the PJTE for non-d0 transition-metal oxyanions.<br>

CONCERNING THE ORTHO SHIFT IN PROTON AND FLUORINE MAGNETIC RESONANCE OF SOME CONJUGATED HYDROCARBONS

1965 ◽  
Vol 43 (8) ◽  
pp. 2392-2397 ◽  
Author(s):  
F. Hruska ◽  
H. M. Hutton ◽  
T. Schaefer
Keyword(s):  
Magnetic Resonance ◽  
Bond Length ◽  
Ionization Potential ◽  
Linear Correlation ◽  
Conjugated Hydrocarbons ◽  
Monosubstituted Benzenes ◽  
First Ionization Potential

A linear correlation with Q is found for the shifts of protons or fluorines placed ortho or cis to the substituent in monosubstituted benzenes, ethylenes, propenes, monofluorobenzenes, and perfluorobenzenes. The substituent X corresponds to H, F, Cl, Br, I, and Q equals P/Ir3 where P is the polarizability of the C—X bond, r is the C—X bond length, and I is the first ionization potential of atom X. The correlation is useful for predicting some as yet unknown shifts in the above compounds. The significance of this correlation is discussed in an inconclusive manner.

Sign in / Sign up

Export Citation Format

Share Document