[(η5‐C5Me5)2 Ti2P6], a Distorted Dimetallaphosphacubane

Scherer, Otto J.; Swarowsky, Herbert; Wolmershäuser, Gotthelf; Kaim, Wolfgang; Kohlmann, Stephan

doi:10.1002/anie.198711531

Cited by 45 publications

(38 citation statements)

References 19 publications

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“…54,[62][63][64][65] Several of the P 6 triple-decker complexes adopt the expected D 6h configuration with a planar P 6 unit, but in the case of 49 a distortion to a chair-like cyclo-hexaphosphido form occurs, and the P 6 ligand binds in a µ 2 :η 3 ,η 3 fashion as a P 6 -6 ligand. Several different geometries can be obtained for P 6 ligands as illustrated by the activation of P 4…”

Section: 77%mentioning

confidence: 99%

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

2010

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Introduction 4164 2. P 4 Activation Leading to P 1 , P 2 , and P 3 Products 4165 2.1. Terminal and Bridging P 1 Ligands from P 4 4165 2.2. Bridging P 2 Ligands from P 4 4166 2.3. Cyclo-P 3 Units Derived from P 4 4168 3. P 4 Activation Leading to P 4 Products 4169 3.1. Coordination of P 4 Tetrahedra 4169 3.2. Rearranged P 4 Products 4169 4. P 4 Activation Leading to P g5 Products 4171 5. Functionalization and Transfer Methodologies 4173 5.1. Functionalization and Subsequent Reactivity of Terminal Monophosphide and Bridging Diphosphorus Complexes Derived from P 4 4173 5.2. Reactivity and Transfer Chemistry of the Cyclo-P 3 Functional Group 4174 5.3. Functionalization and Transfer Chemistry of Polyphosphorus Ligands (P g4 ) Derived from P 4 4175 6. Concluding Remarks 4175 6.1. Conclusions 4175 6.2. Future Prospects 4176 7. Acknowledgments 4176 8. References 4176

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Section: 77%mentioning

confidence: 99%

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

2010

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“…[1] In this context, the isolation of the allphosphorus analogue of one of the most prominent organic molecules-benzene-stabilized in the complex [(Cp*Mo) 2 (m,h 6 :h 6 -P 6 )] (1)i n1 985 by Scherer et al can be viewed as am ilestone in inorganic chemistry. [2] Cyclo-P 6 triple-decker complexes have also been described for Ti,V , Nb,and W. [3][4][5][6][7] Over the last decade,inorganic supramolecules resembling fullerenes were isolated [8][9][10] through coordination of the cyclo-P 5 complexes [Cp R Fe(h 5 -P 5 )] to Cu I halides. Intrigued by the idea of interconnecting cyclo-P 6 complexes 1 to build up as upramolecular inorganic analogue of graphene,wedecided to investigate the coordination chemistry of 1.The described yield of 1 after separation from several other products was only 1%,w hich is probably the reason why no studies on the reactivity of 1 have been carried out over the last 30 years.…”

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confidence: 99%

Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)₂(μ,η⁶:η⁶‐P₆)] Towards the “Naked” Cations Cu⁺, Ag⁺, and Tl⁺

et al. 2015

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Although the cyclo-P6 complex [(Cp*Mo)2(μ,η6:η6-P6)] (1) was reported 30 years ago, little is known about its chemistry. Herein, we report a high-yielding synthesis of 1, the complex 2, which contains an unprecedented cyclo-P10 ligand, and the reactivity of 1 towards the “naked” cations Cu+, Ag+, and Tl+. Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo-P6 middle deck, the [M(1)2]+ complexes are described which show distorted square-planar (M=Cu(4 a), Ag(4 b)) or distorted tetrahedral coordinated (M=Cu(5)) M+ cations. The choice of solvent enabled control over the reaction outcome for Cu+, as proved by powder XRD and supported by DFT calculations. The reaction with Tl+ affords a layered two-dimensional coordination network in the solid state.

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“…Syntheses of metallocenes having increasing number of rings and metals led to triple‐ and multiple‐decker sandwiches complexes 1. A variety of middle rings involving heteroatoms, such as boron, phosphorus, and arsenic, have been synthesized 2–6. The electronic requirements of multiple‐decker sandwiches have traditionally been assessed using molecular orbital (MO) studies of several individual structures.…”

Section: Introductionmentioning

confidence: 99%

“…We have therefore compared TD complexes having P 6 as the middle rings with those containing both C 3 P 3 and B 3 P 3 middle rings. A Sc complex having C 3 P 3 middle ring is the only well characterized complex of a 22 valence electrons (VE) TD complex 6(h)…”

Section: Introductionmentioning

confidence: 99%

Electronic structure and bonding studies on triple‐decker sandwich complexes with a P₆ middle ring

et al. 2006

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DFT and hybrid HF-DFT studies of structure and bonding of CpMP6MCp triple-decker sandwich complexes, ranging from 18-28 valence electrons (VE) with M=Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W, show that the middle P6 ring complexes adopt symmetric planar (28 valence electron count [VEC]), asymmetric planar (26 VEC), and puckered (24 VEC) geometries. According to the mno Rule, 50 skeletal electrons are needed for these triple-decker cluster frameworks. For 28 VEC, this corresponds to 10 electrons more than the 50 electrons of the mno Rule if all VE of the metal are included. These additional electrons control the distortion of a P6 middle ring and other finer structural details. Completely filled 2a* and 2b* orbitals in 28 VE complexes lead to a planar symmetrical P6 middle ring, while the occupancy in either 2a* or 2b* alone explains the in-plane distortions (asymmetric) in 26 VE complexes. In comparison with 28 VE complexes, the puckering of P6 middle ring in 24 VE complexes is due to the greater stabilization of 5a and the extra stabilization of the +4 oxidation state of Ti. The quintet state of 22 VE complexes is planar as 2a* and 2b* are half filled. Similar geometrical and bonding patterns of CpScP6ScCp and C2P3H2ScC3P3H3ScC2P3H2 support the carbon-phosphorus analogy further. The 18 VE systems, CpScC3B3H6ScCp+ and CpScP3B3H3ScCp+, have the 50 skeletal electrons as stipulated by the mno Rule. Corresponding anions have 52 skeletal electrons (20 VE); the middle rings here are distorted in the plane.

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[(η⁵‐C⁵Me₅)₂ Ti₂P₆], a Distorted Dimetallaphosphacubane

Abstract: formed in 90% yield upon reaction of ethyl 8-methoxy-2,7octadienoate 3 with mercury acetate in the presence of calcium oxide and methanol and subsequent reduction with NaBH, (Scheme 1).

Cited by 45 publications

References 19 publications

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)₂(μ,η⁶:η⁶‐P₆)] Towards the “Naked” Cations Cu⁺, Ag⁺, and Tl⁺

Electronic structure and bonding studies on triple‐decker sandwich complexes with a P₆ middle ring

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[(η5‐C5Me5)2 Ti2P6], a Distorted Dimetallaphosphacubane

Abstract: formed in 90% yield upon reaction of ethyl 8-methoxy-2,7octadienoate 3 with mercury acetate in the presence of calcium oxide and methanol and subsequent reduction with NaBH, (Scheme 1).

Cited by 45 publications

References 19 publications

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2(μ,η6:η6‐P6)] Towards the “Naked” Cations Cu+, Ag+, and Tl+

Electronic structure and bonding studies on triple‐decker sandwich complexes with a P6 middle ring

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[(η⁵‐C⁵Me₅)₂ Ti₂P₆], a Distorted Dimetallaphosphacubane

Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)₂(μ,η⁶:η⁶‐P₆)] Towards the “Naked” Cations Cu⁺, Ag⁺, and Tl⁺

Electronic structure and bonding studies on triple‐decker sandwich complexes with a P₆ middle ring