1,2-Diphosphinobenzene as a synthon for the 1,2,3-triphospha- and 2-arsa-1,3-diphosphaindenyl anions and a stable organo derivative of the P8 unit of Hittorf’s phosphorus

Green, Michael; Hooper, Thomas N.; Kilby, Richard J.; McGrady, John E.; Pantazis, Dimitrios A.; Russell, Christopher A.

doi:10.1039/b717204d

Cited by 36 publications

(45 citation statements)

References 24 publications

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“…with cyclopentadienyl iron or iridium carbonyl species (Barr et al, 1991;Scheer et al, 1996), and in the tricyclic [3.3.0.0 3,7 ]octaphosphane (Butts et al, 2008). Huang and Diaconescu (2012).…”

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confidence: 99%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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Rare earth chemistry has witnessed remarkable advances in recent years. In particular, ancillary ligands other than cyclopentadienyl derivatives have been introduced to the organometallic chemistry and their complexes exhibit distinct reactivity and properties compared to the metallocene or half-sandwiched analogues. The present chapter reviews arene-bridged rare earth complexes with an emphasis on those compounds obtained by reduction reactions. A particular emphasis is placed on rare earth complexes supported by 1,1′-ferrocenediyl diamides since they show the most diverse chemistry with arenes: fused arenes, such as naphthalene and anthracene, formed inverse-sandwiched complexes, in which the arene is dianionic; weakly conjugated arenes, such as biphenyl, p-terphenyl, and 1,3,5-triphenylbenzene, were unexpectedly reduced by four electrons and led to 6-carbon, 10- electron aromatic systems; on the contrary, (E)-stilbene, which has a carbon-carbon double bond between the two phenyl rings, could only be reduced by two electrons, which were located on the carbon-carbon double bond instead of the phenyl rings.

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confidence: 99%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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“…[6] The p-electron delocalisation is severely affected by the large differences in the energies of the p orbitals from C, P and Sn involved in the p bonding. One major consequence of this can be anticipated in the ligating properties of these rings: the recently reported structure for the dilithio salt of the C 6 H 4 P 2 Sn 2À di-A C H T U N G T R E N N U N G anion, [8] for example, has a different h…”

Section: Dianionic Isomers Of Sncmentioning

confidence: 99%

“…[6][7][8][9][10][11] They also can exhibit enhanced p-acceptor properties, such as in the cases of 1,2,4-or 1,2,3-triphospholide anions [4,6,7] and the 1,2,3-triphosphaindenyl anion C 6 H 4 P 3 À . The last of these is prepared by the simple procedure of deprotonation of 1,2-diphosphinobenzene with nBuLi followed by treatment with PCl 3 [6] or SbA C H T U N G T R E N N U N G (NMe 2 ) 3 [7] in the presence of [Li[12]crown-4) 2 ]…”

Section: Introductionmentioning

confidence: 99%

“…[6] The heavier atoms Sb or Sn each have predominant lonepair orbitals largely of s character and s and p bonds are formed predominantly by involving p orbitals. In the case of Sn, the p donation into the vacant orbital of the two-coordinate Sn II centre makes it a substantial new class of Arduengo-type carbenes.…”

Section: Introductionmentioning

confidence: 99%

“…Other isoelectronic analogues are prepared by deprotonation of 1,2-(YH 2 ) 2 C 6 H 4 (Y = N, P) with nBuLi/EA C H T U N G T R E N N U N G (NMe 2 ) m (E = Sn, Sb and m = 2, 3) in the presence of N,N,N',N'-tetramethylethylenediamine (TMEDA) as the solvent. [8] This procedure also affords sideproducts, such as Hittorfs phosphorus [6] or Zintl-type [9] ions [Sb 7 {Li 3 ·6 NHMe 2 }]. [2] The diphosphoindenyl ions are also isoelectronic with dithiazolyl radicals [10] and triazolyl anions, [11] which have been extensively used in magnetic storage devices and in coordination chemistry, respectively.…”

Section: Introductionmentioning

confidence: 99%

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Structure and Bonding in Stannadiphospholes and their Dianions SnC₂P₂R₂^m (R=H, tBu m=0, −2): A Comparative Study with C₅H₅⁺ and C₅H₅⁻ Analogues

Reddy

Usharani

Nixon

et al. 2011

Chemistry A European J

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The potential energy surfaces of both neutral and dianionic SnC(2)P(2)R(2) (R=H, tBu) ring systems have been explored at the B3PW91/LANL2DZ (Sn) and 6-311+G* (other atoms) level. In the neutral isomers the global minimum is a nido structure in which a 1,2-diphosphocyclobutadiene ring (1,2-DPCB) is capped by the Sn. Interestingly, the structure established by X-ray diffraction analysis, for R=tBu, is a 1,3-DPCB ring capped by Sn and it is 2.4 kcal mol(-1) higher in energy than the 1,2-DPCB ring isomer. This is possibly related to the kinetic stability of the 1,3-DPCB ring, which might originate from the synthetic precursor ZrCp(2)tBu(2)C(2)P(2). In the case of the dianionic isomers we observe only a 6π-electron aromatic structure as the global minimum, similarly to the cases of our previously reported results with other types of heterodiphospholes. The existence of large numbers of cluster-type isomers in neutral and 6π-planar structures in the dianions SnC(2)P(2)R(2)(2-) (R=H, tBu) is due to 3D aromaticity in neutral clusters and to 2D π aromaticity of the dianionic rings. Relative energies of positional isomers mainly depend on: 1) the valency and coordination number of the Sn centre, 2) individual bond strengths, and 3) the steric effect of tBu groups. A comparison of neutral stannadiphospholes with other structurally related C(5)H(5)(+) analogues indicates that Sn might be a better isolobal analogue to P(+) than to BH or CH(+). The variation in global minima in these C(5)H(5)(+) analogues is due to characteristic features such as 1) the different valencies of C, B, P and Sn, 2) the electron deficiency of B, 3) weaker pπ-pπ bonding by P and Sn atoms, and 4) the tendency of electropositive elements to donate electrons to nido clusters. Unlike the C(5)H(5)(+) systems, all C(5)H(5)(-) analogues have 6π-planar aromatic structures as global minima. The differences in the relative ordering of the positional isomers and ligating properties are significant and depend on 1) the nature of the π orbitals involved, and 2) effective overlap of orbitals.

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Die Chemie von niedrig koordiniertem Phosphor

Russell

2009

Angewandte Chemie

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Die jüngsten Entwicklungen bei Verbindungen mit niedrig koordiniertem Phosphor zeigen klar, dass dieses Element noch immer voller Überraschungen steckt. Beispielsweise diente die Substitution von CR durch P bei neuen Phosphaalkinen dazu, mutmaßliche Intermediate einer wichtigen Transformation zu stabilisieren und neuartige Diphosphacyclobutadien‐Sandwich‐Komplexe herzustellen (siehe Schema).

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1,2-Diphosphinobenzene as a synthon for the 1,2,3-triphospha- and 2-arsa-1,3-diphosphaindenyl anions and a stable organo derivative of the P8 unit of Hittorf’s phosphorus

Cited by 36 publications

References 24 publications

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Structure and Bonding in Stannadiphospholes and their Dianions SnC₂P₂R₂^m (R=H, tBu m=0, −2): A Comparative Study with C₅H₅⁺ and C₅H₅⁻ Analogues

Die Chemie von niedrig koordiniertem Phosphor

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1,2-Diphosphinobenzene as a synthon for the 1,2,3-triphospha- and 2-arsa-1,3-diphosphaindenyl anions and a stable organo derivative of the P8 unit of Hittorf’s phosphorus

Cited by 36 publications

References 24 publications

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Structure and Bonding in Stannadiphospholes and their Dianions SnC2P2R2m (R=H, tBu m=0, −2): A Comparative Study with C5H5+ and C5H5− Analogues

Die Chemie von niedrig koordiniertem Phosphor

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Structure and Bonding in Stannadiphospholes and their Dianions SnC₂P₂R₂^m (R=H, tBu m=0, −2): A Comparative Study with C₅H₅⁺ and C₅H₅⁻ Analogues