A Main‐Group Analogue of Housene: The Subtle Influence of the Inert‐Pair Effect in Group 15 Clusters

Fish, Cheryl; Green, Michael; Jeffery, John C.; Kilby, Richard J.; Lynam, Jason M.; McGrady, John E.; Pantazis, Dimitrios A.; Russell, Christopher A.; Willans, Charlotte E.

doi:10.1002/anie.200601804

Cited by 37 publications

(19 citation statements)

References 25 publications

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“…7 has an envelope-type structure (Fig. 1), superficially similar to the one we have previously reported 11 for the Sb(III) analogue ClSbP 2 (CBu t ) 2 , 2 (Scheme 1), but a close examination of these two structures reveals significant differences. The most conspicuous of these is that the distinct inward tilt of the apical SbCl unit observed in 2, which we have argued is indicative of incipient nido cluster character ([SbP 2 (CBu t ) 2 ] + Cl − ), 11 is completely absent in 7 .…”

Section: Computational Analysissupporting

confidence: 77%

Promotion of phosphaalkyne cyclooligomerisation by a Sb(v) to Sb(iii) redox process

et al. 2008

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A high yield of the tetraphosphaladderene, anti-tetraphosphatricyclo[4.2.0.0(2,5)]octa-3,7-diene, is obtained from reaction of the zirconocene 1,3-diphosphabicyclo[1.1.0]butane with Ph(2)SbCl(3) in THF or CH(2)Cl(2). Exploration of the reaction pathway using density functional theory suggests that an envelope-type adduct of Ph(2)SbCl and 1,3-diphosphabicyclo[1.1.0]butane plays a pivotal role in the reaction. The zwitterionic character of this intermediate species allows it to act simultaneously as both an ene and an eneophile, and a symmetry-allowed bimolecular reaction leads to the tetraphosphaladderene species via a spirocyclic intermediate.

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Section: Computational Analysissupporting

confidence: 77%

Promotion of phosphaalkyne cyclooligomerisation by a Sb(v) to Sb(iii) redox process

et al. 2008

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“…In these structures, the bridgehead P has two lone pairs, and CH and BH have just one lone pair. Envelope structures have also been found as intermediates in the interconversion between a nido (cationic) and planar cyclic (anionic) structure, as in the synthesis of a Sb t Bu 2 C 2 P 2 species, which has an envelope ClSb t Bu 2 C 2 P 2 45. The high energies of the 15 a ′– d ′ isomers and their potential rearrangement to cyclic planar 12 a ′ , b ′ , g ′, and k ′ hints that they might also be intermediates in the conversion of a neutral nido structure to a dianionic cyclic geometry (Scheme , bottom).…”

Section: Resultsmentioning

confidence: 99%

Electronic Structure and Bonding in Neutral and Dianionic Boradiphospholes: R′BC₂P₂R₂ (R=H, tBu, R′=H, Ph)

Usharani

Poduska

Nixon

et al. 2009

Chemistry A European J

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Classical and non-classical isomers of both neutral and dianionic BC(2)P(2)H(3) species, which are isolobal to Cp(+) and Cp(-), are studied at both B3LYP/6-311++G(d,p) and G3B3 levels of theory. The global minimum structure given by B3LYP/6-311++G(d,p) for BC(2)P(2)H(3) is based on a vinylcyclopropenyl-type structure, whereas BC(2)P(2)H(3)(2-) has a planar aromatic cyclopentadienyl-ion-like structure. However, at the G3B3 level, there are three low-energy isomers for BC(2)P(2)H(3): 1) tricyclopentane, 2) nido and 3) vinylcyclopropenyl-type structures, all within 1.7 kcal mol(-1) of each other. On the contrary, for the dianionic species the cyclic planar structure is still the minimum. In comparison to the isolobal Cp(+) and H(n)C(n)P(5-n)(+) isomers, BC(2)P(2)H(3) shows a competition between pi-delocalised vinylcyclopropenyl- and cluster-type structures (nido and tricyclopentane). Substitution of H on C by tBu, and H on B by Ph, in BC(2)P(2)H(3) increases the energy difference between the low-lying isomers, giving the lowest energy structure as a tricyclopentane type. Similar substitution in BC(2)P(2)H(3)(2-) merely favours different positional isomers of the cyclic planar geometry, as observed in 1) isoelectronic neutral heterodiphospholes EtBu(2)C(2)P(2) (E = S, Se, Te), 2) monoanionic heterophospholyl rings EtBu(2)C(2)P(2) (E = P(-), As(-), Sb(-)) and 3) polyphospholyl rings anions tBu(5-n)C(n)P(5-n) (n = 0-5). The principal factors that affect the stability of three-, four-, and five-membered ring and acyclic geometrical and positional isomers of neutral and dianionic BC(2)P(2)H(3) isomers appear to be: 1) relative bond strengths, 2) availability of electrons for the empty 2p boron orbital and 3) steric effects of the tBu groups in the HBC(2)P(2)tBu(2) systems.

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“…Stannylated 1,3‐diphosphacyclobutenes were reported by Regitz and co‐workers . An unusual 1,3‐diphosphacyclobutene compound ClSb(P 2 C 2 t Bu 2 ) with a side‐on coordinated SbCl unit was obtained by Russel and co‐workers by treatment of [Cp 2 Zr(P 2 C 2 t Bu 2 )] with SbCl 3 . The 1,3‐diphosphacyclobutene ligand in 1 is clearly η 3 ‐coordinated (Co1−P1 2.180(2), Co1−P2 2.300(2), Co1−C1 3.051(1), Co1−C2 2.010(5) Å) with a fold angle around the P1–P2 vector of 34.3°.…”

Section: Resultsmentioning

confidence: 97%

1,3‐Diphosphacyclobutene Cobalt Complexes

Rödl

Schwedtmann

Weigand

et al. 2019

Chemistry A European J

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The synthesis andc haracterization of rare 1,3-diphosphacyclobutene transition-metal complexes is described. Reactions of the cobalt-hydride complex [Co(P 2 C 2 tBu 2 ) 2 H] (G)w ith nBuLi, tBuLi, or PhLi afforded [Li-(solv) x {Co(h 3 -P 2 C 2 tBu 2 HR)(h 4 -P 2 C 2 tBu 2 )}] (1:R = nBu, (solv) x = (Et 2 O) 2 ; 2:R = tBu, (solv) x = (thf) 2 ; 3:R = Ph, (solv) x = (Et 2 O)(thf) 2 ), with an h 3 -coordinated 1,3-diphosphacyclobutene ligand as ar esult of organyl-anion attacka to ne of the phosphorus atoms of the bis(1,3-diphosphacyclobutadiene) backbone. In contrast to the reactions with PhLi, the arylmagnesium compounds p-tolyl magnesium chloride and p-fluorophenyl magnesiumbromide deprotonate [Co(P 2 C 2 tBu 2 ) 2 H] to give the magnesium salt [Mg(MeCN) 6 ] [Co(h 4 -P 2 C 2 tBu 2 ) 2 ] 2 (4), whichc ontainsabis(1,3-diphosphacyclobutadiene)-cobaltatea nion. The [Co(h 4 -P 2 C 2 tBu 2 ) 2 ] À anions are well separated from the octahedral [Mg(MeCN) 6 ] 2 + cationi nt he molecular structure of 4.C ompound 1 reacts with Me 3 SiCl to give neutral [Co(h 3 -P 2 C 2 tBu 2 HnBu)(h 4 -P 2 C 2 tBu 2 SiMe 3 )] (5,5 2% yield) with an SiMe 3 group attached to one of the Pa toms of the previously unfunctionalized backbone. Figure 1. Previously reported derivatizations of 1,3-diphosphacyclobutadiene complexes through the attack of nucleophiles. [7][8][9] [a] C. Rçdl,P rof. Dr.R.W olf Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.Figure 2. a) FunctionalizationofF by treatment with electrophiles (previous work): i) HCl·Et 2 O;ii)MeI ;iii)Ph 2 PCl ;b)synthesis of anionic 1,3-diphosphacyclobutenec omplexes 1-3 by addition of lithium organyls to G (this work).

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A Main‐Group Analogue of Housene: The Subtle Influence of the Inert‐Pair Effect in Group 15 Clusters

Cited by 37 publications

References 25 publications

Promotion of phosphaalkyne cyclooligomerisation by a Sb(v) to Sb(iii) redox process

Promotion of phosphaalkyne cyclooligomerisation by a Sb(v) to Sb(iii) redox process

Electronic Structure and Bonding in Neutral and Dianionic Boradiphospholes: R′BC₂P₂R₂ (R=H, tBu, R′=H, Ph)

1,3‐Diphosphacyclobutene Cobalt Complexes

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A Main‐Group Analogue of Housene: The Subtle Influence of the Inert‐Pair Effect in Group 15 Clusters

Cited by 37 publications

References 25 publications

Promotion of phosphaalkyne cyclooligomerisation by a Sb(v) to Sb(iii) redox process

Promotion of phosphaalkyne cyclooligomerisation by a Sb(v) to Sb(iii) redox process

Electronic Structure and Bonding in Neutral and Dianionic Boradiphospholes: R′BC2P2R2 (R=H, tBu, R′=H, Ph)

1,3‐Diphosphacyclobutene Cobalt Complexes

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Electronic Structure and Bonding in Neutral and Dianionic Boradiphospholes: R′BC₂P₂R₂ (R=H, tBu, R′=H, Ph)