Intramolecular Phosphine−Phosphine Donor−Acceptor Complexes

Wawrzyniak, Piotr; Fuller, Amy L.; Slawin, Alexandra M. Z.; Kilián, Petr

doi:10.1021/ic801833a

Cited by 61 publications

(101 citation statements)

References 31 publications

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“… of bay angles b 373.5(7) 373.4 (9) 373 (3) 375 (1) 375.4 (7) 373.4 (6) Splay angle 13.5(7) 13.4 (9) 13 (3) 15 (1) 15.4 (7) 13.4 (6) Out-of-plane displacement Te1-C1-C9-P The phosphorus-tellurium peri-distances P···Te1 are in the range of 3.090(1) Å (2) and 3.205(2) Å (4a) and are thus significantly shorter than to the sum of the van der Waals radii (r vdw ) of phosphorus 7 and tellurium (3.86 Å) 22 (80 % of the r vdw for 2, 83 % for 4a). is a common length observed for a P-C single bond, especially in similar systems (e.g.…”

Section: 8(2)mentioning

confidence: 99%

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Peri-Substituted Phosphorus–Tellurium Systems–An Experimental and Theoretical Investigation of the P···Te through-Space Interaction

et al. 2015

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DEDICATION: Dedicated to Wolf-Walther du Mont on the occasion of his 70 th birthday.KEYWORDS: peri-substitution, phosphorus-tellurium, through-space spin-spin coupling, acenaphthene 2 ABSTRACT: A series of peri-substituted phosphorus-tellurium systems R'Te-Acenap-PR 2 (R' = Ph, pAn, Nap, Mes, Tip; R = i Pr, Ph) exhibiting large "through space" spin-spin coupling constants and the "onset" of three-centre four-electron type interactions are presented. The influence of the substituents at the phosphorus and tellurium atoms as well as their behavior upon oxidation (with S, Se) or metalcoordination (Pt, Au) is discussed using NMR spectroscopy, single crystal X-ray diffraction, and advanced DFT studies including NBO, AIM and ELI-D analyses.

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Section: 8(2)mentioning

confidence: 99%

“…1.846(4) Å for one of the starting materials, the peri-substituted Br, P i Pr 2 ). 26,27 The acenaphthene skeleton of the systems is mainly planar with the central acenaphthene ring torsion angles (e.g. C6-C5-C10-C1 and C4-C5-C10-C9) being close to 180°.…”

Section: 8(2)mentioning

confidence: 99%

Peri-Substituted Phosphorus–Tellurium Systems–An Experimental and Theoretical Investigation of the P···Te through-Space Interaction

et al. 2015

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“…It is noteworthy that indirect spin−spin coupling constants (SSCC) involving the nuclei 31 22 The 31 P NMR spectrum of 6 shows a characteristic J( 31 P− 31 P) coupling of 389 Hz, which compares well with that of V (364 Hz). 9 It is noteworthy that the 1 J( 31 P− 13 C) coupling constants significantly decreases from ArBCl 2 (1) to ArInCl 2 (4) and from ArPCl 2 (6) to ArSbCl 2 (9), especially on comparison of elements from period 4 to 5 (1 (61/65 Hz) > 2 (49/48 Hz) > 3 (50/51 Hz) > 4 (27/25 Hz); 6 (75/68 Hz) > 7 (68/62 Hz) > 8 (18/19 Hz)).…”

Section: Organometallicsmentioning

confidence: 99%

Probing Donor–Acceptor Interactions in peri-Substituted Diphenylphosphinoacenaphthyl–Element Dichlorides of Group 13 and 15 Elements

et al. 2014

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Transmetalation reactions of ArLi with ECl 3 (E = Al, P, In, Bi) and ArSnBu 3 with ECl 3 (E = B, Ga, Tl, As, Sb) gave rise to the formation of peri-substituted diphenylphosphinoacenaphthyl−element dichlorides ArECl 2 (Ar = 6-Ph 2 PAce-5-), which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. DFT calculations were performed on the compounds at relaxed gas-phase molecular geometries. For the series ArECl 2 containing group 13 elements one structure type featuring regular Lewis pairs with short E−P peri distances (E = B, Al, Ga, In, Tl) was observed. For the series ArECl 2 containing group 15 elements two structural types with very different peri distances (E = P, As, Sb, Bi) were found. The computed electron and pair densities were topologically analyzed according to the atoms-in-molecules (AIM) and electron localizability indicator (ELI-D) spacepartitioning schemes, which facilitates the characterization of the peri interactions and also allows for monitoring minute electronic effects induced by different substituents and/or spatial arrangements. ■ INTRODUCTIONDonor−acceptor interactions between phosphines and maingroup elements have received tremendous interest, 1 which has been recently fueled by the discovery that bulky phosphines and boranes may form frustrated Lewis pairs (FLPs) that are able to activate small molecules, such as dihydrogen and carbon dioxide, without the aid of a transition metal. 2 Peri-substituted (ace)naphthylphosphinoboranes comprise regular Lewis pairs or FLPs depending on the nature of the substituents attached to the B and P atoms in 1,8-and 5,6-positions (Chart 1). Sasamori and Tokitoh et al. 3 communicated two 1-dichlorophosphino-8-naphthyl-diarylboranes 1-(Cl 2 P)-8-(R 2 B)-Nap (Ia, R = 3,5-t-Bu 2 C 6 H 3 ; Ib, R = Mes) and later disclosed structural data. 4 Reduction of Ia,b with Mg proceeded with aryl group migration and gave rise to the formation of unique phosphaboranes. 3 Miqueu and Bourissou et al. 5 reported on the three 1-diisopropylphosphino-8-naphthyl-diorganoboranes 1-(iPr 2 P)-8-(R 2 B)-Nap (IIa, R = Mes; IIb, R = Cy; IIc, R 2 = Flu; Flu = 2,2′-biphenylene), which were structurally elucidated. The different P−B peri distances (Å) of 2.108(2) (Ia), 2.892(2) (Ib), 2.173(3) (IIa), 2.076(2) (IIb), and 2.011(2) (IIc) demonstrate that the bulk and electronic effect of the substituents attached to the B and P atoms determines the nature of the peri interaction: namely, if it is dominated by attractive or repulsive forces.Our group described 1-diphenylphosphino-8-naphthyl-dimesitylborane (1-(Ph 2 P)-8-(Mes 2 B)-Nap, IIIa) and the closely related 5-diphenylphosphino-6-acenaphthyl-dimesitylborane (5-(Ph 2 P)-6-(Mes 2 B)-Ace, IIIb), possessing the same substituents at the B and P atoms with albeit quite different B−P peri distances of 2.162(2) and 3.050(3) Å, which is due to the fact that the naphthyl framework accommodates a higher degree of conformational flexibility in comparison to the rigid acenaphthyl framework. 6 Wang et al. also conducted an ...

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“…22 This is presumably due to the tedious preparation of the basic starting materials, namely, 1,8-dihalonaphthalenes. Replacing the latter by the easily accessible 5,6-dihaloacenaphthenes has paved the way for the preparation of 6-diorganophosphinoacenaphthyl-5-element compounds, 23 including the stannanes C, in which the Sn−P interaction is either repulsive or attractive depending on the Lewis acidity of the Sn atoms. 24−26 As part of our systematic studies on the bond situation in peri-substituted diphenylphosphino(ace)-naphthyl element compounds, we have now investigated a series of sterically congested 5-diphenylphosphinoacenaphth-6-yl-silanes and -silanols.…”

Section: ■ Introductionmentioning

confidence: 99%

Sterically Congested 5-Diphenylphosphinoacenaphth-6-yl-silanes and -silanols

et al. 2015

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The synthesis and characterization of the 5-diphenylphosphinoacenaphth-6-yl-silanes 5-Ph 2 P-Ace-6-SiMe 2 H (1), 5-Ph 2 P(S)-Ace-6-SiMe 2 H (1S), 5-Ph 2 P(Se)-Ace-6-SiMe 2 H (1Se), and 5-Ph 2 P-Ace-6-SiMe 2 Cl (2) as well as of the 5-diphenylphosphinoacenaphth-6-yl-silanols 5-Ph 2 P-Ace-6-SiMe 2 OH (3), 5-Ph 2 P(O)-Ace-6-SiMe 2 OH (3O), 5-Ph 2 P(S)-Ace-6-SiMe 2 OH (3S), and 5-Ph 2 P(Se)-Ace-6-SiMe 2 OH (3Se) are reported. Due to steric congestion in the bay area, the substituents in peri-positions are affected by repulsion, out-of-plane deflection, and distortion of the spatial arrangement to various extents. The peri-interaction energy associated with the steric congestion of these and a number of previously known reference compounds was computationally estimated with a set of isodesmic reactions. The organo-H-silanes 1, 1S, and 1Se possess very weak intramolecular hydrogen bridges of the types Si−H···P and Si−H···EP (E = S, Se), whereas the organosilanols 3O, 3S, and 3Se contain medium-strength hydrogen bonds of the type Si−OH···EP (E = O, S, Se). These hydrogen bonds and those of related model complexes H 3 SiOH···(E)PH 3 were analyzed applying real-space bonding indicators derived from the electron and pair densities using the atoms-in-molecules and electron localizability indicator space-partitioning schemes as well as natural population analysis and natural bond orbital analyses.

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Intramolecular Phosphine−Phosphine Donor−Acceptor Complexes

Cited by 61 publications

References 31 publications

Peri-Substituted Phosphorus–Tellurium Systems–An Experimental and Theoretical Investigation of the P···Te through-Space Interaction

Peri-Substituted Phosphorus–Tellurium Systems–An Experimental and Theoretical Investigation of the P···Te through-Space Interaction

Probing Donor–Acceptor Interactions in peri-Substituted Diphenylphosphinoacenaphthyl–Element Dichlorides of Group 13 and 15 Elements

Sterically Congested 5-Diphenylphosphinoacenaphth-6-yl-silanes and -silanols

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