Tangent-sphere models of molecules. III. Chemical implications of inner-shell electrons

Bent, Henry A.

doi:10.1021/ed042p302

Cited by 11 publications

(8 citation statements)

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“…This method of calculating R implies that the decrease in bond length in going from methyl phosphine to methyl sulfide to methyl chloride should directly reflect the decrease in core size in going from phosphorus to sulfur to chlorine. The latter changes are 0.05 and 0.04 A, respectively; the corresponding bond-length changes [Table 1, Part III (2) ] are 0.040 and 0.034A.…”

Section: The R Equationmentioning

confidence: 99%

“…In Part III (2) the model was extended to compounds that contain second-row elements. The supposition in these cases of large atomic cores, combined with Linnett's suggestion regarding the tendency of electrons in different spin sets to become anti coincident (3), was found to yield simple explanations for such wellknown features of the chemistry of second-row (and later) elements as the occurrence of near-90°valence angles; lengthened bonds and lowered ionization potentials; expanded octets; enhanced reactivity toward nucleophilic reagents (more generally, heightened 17-donor properties and 7r-acceptor properties) the scarcity of multiple bonds to other second-row elements; the low basicity of attached lone pairs; and (less well known) several anomalous bond-length trends, for which a semiquantitative explanation was offered.…”

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confidence: 99%

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Tangent-sphere models of molecules. IV. Estimation of internuclear distances; The electronic structure of metals

Bent¹

1965

J. Chem. Educ.

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Section: The R Equationmentioning

confidence: 99%

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confidence: 99%

Tangent-sphere models of molecules. IV. Estimation of internuclear distances; The electronic structure of metals

Bent¹

1965

J. Chem. Educ.

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“…1981 Linnett himself originally presented LDQ theory as a simple modification of Lewis' original bonding concepts (8). Like both the two-dimensional topological Lewis structures themselves, and their three-dimensional extensions in terms of the tangent sphere model (9)(10)(11)(12)(13)(14) and the VSEPR rules (15), LDQ theory makes use of such concepts as the octet rule (for period 2 elements), the electroneutrality principle (in terms of favorable formal charge distributions), and the isoelectronic principle, as well as assorted electrostatic arguments common to all such localized bonding models. Its sole innovation is its use of the postulate of the two tetrahedral spin sets to account for the effects of the Pauli principle and its attempt to maximize their degree of correlation within the bounds set by the other electrostatic energy components.…”

Section: To Point Tomentioning

confidence: 99%

“…However, in so doing, LDQ theory does not deny the existence of nuclear-nuclear repulsions nor that they play a role in determining the finer details of structure and reactivity (or, indeed, a major role in the case of ionic species). Bent, for example, has made a number of specific applications of nuclear-nuclear repulsions within the context of LDQ theory in order to rationalize certain trends in bond angles and bond lengths (9)(10)(11)(12)(13)(14), and Firestone has called attention to a number of situations in which it is not possible to arrive at a satisfactory disposition of the tetrahedral spin sets without simultaneously moving bonding electrons away from the regions of the nuclear-nuclear axes (2,3). This frequently occurs in the case of transition state species and the resulting destabilization, due to the increase in nuclear-nuclear repulsions and the decrease in electron-nuclear attractions, has been termed Linnett or L strain by Firestone and has been used by him to analyze the origin of activation energies in the case of E2, SH2, and S,2 reactions (17).…”

Section: To Point Tomentioning

confidence: 99%

Some comments on Linnett Double Quartet theory

Jensen¹

1981

Can. J. Chem.

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(1) ple, Dale (4) in his summary of LDQ theory lists, in which purports to be a critical reexamination and addition to the postulates dealing with electronic evaluation of the application of Linnett Double charge and spin correlation, the following two adQuartet (LDQ) theory to problems of structure, ditional postulates. (1) "The attraction between reactivity, and resonance in organic chemistry. electrons and atomic nuclei tends to draw a maxiThis article presents an interpretation of LDQ mum number of electrons to regions between theory which is, in the present writer's opinion, atoms." (2) "Two electrons of opposite spin may incorrect and potentially misleading for those read-occur together as a pair (coincidence) when more ers who are only superficially acquainted with Lin-electrons can thereby be concentrated between two nett's work. Consequently, it is felt that some atoms to form a bond." Likewise, Lawless and comments on this interpretation are in order. On Smith (5) state the underlying principles of LDQ the other hand, the article does call attention to a theory to be that "electrons are electrostatically number of situations which, though far from in-attracted by the nuclei, are mutually repelled by validating LDQ theory as the authors contend, do other electrons, and have a tendency to achieve a point to a need for a more explicit consideration of fairly uniform charge distribution in a given cheminuclear-nuclear repulsions in certain qualitative cal species, as limited by the effect of the spin wave applications of the theory. Such a treatment is made function and relative electronegativities of the in the present paper and is shown both to resolve atoms involved." the problems raised by Langler et al. and to point to In both statements the nuclei are assigned a key a new area of application for Firestone's theory of role. Structures are a result of the dynamic interLinnett or L strain (2,3).play between the desire of the electrons, on the one hand, to reduce their mutual repulsions by mainThe Role of the Nuclei in LDQ Theory taining their spin sets and as much anticoincidence The major source of difficulty with the authors' between the sets as possible, and the desire of the interpretation of LDQ theory stems from their mis-nuclei, on the other hand, to increase their electron conceptions about its primary postulates. After attractions and reduce nuclear-nuclear repulsions first describing the concept of two tetrahedral spin by concentrating as many electrons as possible sets, the authors summarize the theory as follows: along the internuclear axes. Indeed, the role of the "Molecular structures are elaborated by maximiz-nuclei is assumed to be so apparent from traditional ing electronic separations and minimizing elec-bonding concepts that the two standard books on tronic repulsions. Priority, it is assumed, must be LDQ theory by Luder (6) and Linnett (7) do not given to maximizing the separation of electrons even explicitly state postulates dealing with these having the same spin." This is corre...

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“…Additionally, the diffused and polarizable character of sulfur's unshared electrons accounts for the generally small bond angles at sulfur, compared to oxygen 45 (cited in Ch. 6; see Fig.…”

Section: Chemical Implicationsmentioning

confidence: 99%