Solid-state conformations of compounds (arene)L2MP(C6H5)3 and (arene)LL'MP(C6H5)3

Brunner, Henri; Hammer, Benedikt; Krueger, C.; Angermund, Klaus; Bernal, Ivan

doi:10.1021/om00125a019

Cited by 26 publications

(19 citation statements)

References 5 publications

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“…In a 1983 paper, we showed that in half-sandwich compounds [(π-Ar)LL′MPPh 3 ] there is an additional rotation about the P-M bond, differentiating the gauche phenyl rings into close and distant to π-Ar ( C in Figure 1). 1 The phenyls close to π-Ar have rotation angles |0 < ρ < 60°|, and the phenyls distant to π-Ar have |60 < ρ < 120°|. Subsequently, we will show that this rotation is part of bonding motif Ph PPh 3 face-on π-Ar.…”

Section: Introductionmentioning

confidence: 69%

“…This rotation brings the gauche phenyl |0 < ρ < 60°| close and face-on toward π-Ar, whereas the gauche phenyl |60 < ρ < 120°| becomes distant and edge-on toward π-Ar. It was argued that the steric hindrance of the π-Ar ligand with the ortho -CH bond of the edge-exposed phenyl is responsible for the rotation, 1 which is wrong (see below).…”

Section: Results and Discussionmentioning

confidence: 99%

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PPh₃ Propeller Diastereomers: Bonding Motif Ph_PPh₃ Face-On π-Ar in Half-Sandwich Compounds [(π-Ar)LL′MPPh₃]

et al. 2018

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Chiral-at-metal compounds ( R Ru , S C )/( S Ru , S C )-[CyRu(1O-2N)PPh 3 ]PF 6 and ( R Ru , S C )/( S Ru , S C )-[CyRu(2O-1N)PPh 3 ]PF 6 were prepared using anions 1O-2N – and 2O-1N – of the Schiff bases, derived from the hydroxynaphthaldehydes and ( S )-1-phenylethylamine. The pure ( R Ru , S C )-diastereomers were obtained by crystallization. In the unit cell of ( R Ru , S C )-[CyRu(1O-2N)PPh 3 ]PF 6 , there are three independent molecules, which differ in the propeller sense of the PPh 3 ligand. Molecules [1] and [2] have ( M PPh 3 )-configuration and molecule [3] has ( P PPh 3 )-PPh 3 configuration. PPh 3 diastereoisomerism is discussed including other pairs of compounds, differing only in the PPh 3 configuration. A conformational analysis reveals an internal stabilization inside the PPh 3 ligand by a system of attractive CH/π interactions and a new bonding motif Ph PPh 3 face-on π-Ar, both characteristic features of [(π-Ar)LL′MPPh 3 ] compounds. The propeller diastereomers interconvert via a low-energy pathway and a high-energy pathway, corroborated by density functional theory calculations.

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Section: Introductionmentioning

confidence: 69%

Section: Results and Discussionmentioning

confidence: 99%

PPh₃ Propeller Diastereomers: Bonding Motif Ph_PPh₃ Face-On π-Ar in Half-Sandwich Compounds [(π-Ar)LL′MPPh₃]

et al. 2018

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“…They do not use their rotational degrees of freedom, but in the 1:1 co‐crystal set up an image/mirror image arrangement. This is also obvious from the chirality torsion angles Fe–P–C i –C o >90°, which describe the chirality of M–P–phenyl systems (Table ) . Plus and minus of the torsion angle define the phenyl chirality as ( P ) and ( M ) …”

Section: Resultsmentioning

confidence: 98%

Co‐Crystallization of Half‐Sandwich (R_M,R_C)/(S_M,R_C) Diastereomers in Single Crystals

et al. 2016

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Diastereomer separation by fractional crystallization is the most important method for the resolution of enantiomers in research as well as in industry. Herein we describe two different types of diastereomer co-crystallization, which impede diastereomer separation. The two diastereomers (R Fe ,R C )-and (S Fe ,R C )-[CpFe(Prophos)PPh(OMe) 2 ]PF 6 , differing only in the metal atom configuration, form 1:1 co-crystals with a racematelike lattice. Between the (R Fe ,R C ) and (S Fe ,R C ) diastereomers there is an "almost"-inversion center and the (R Fe ,R C )/(S Fe ,R C ) pair repeats as a kind of "dimer" in the lattice. Crystallization of a [a] General: 1 H/ 13 C/ 31 P{ 1 H} NMR: Bruker Avance 400 (400/125/ 162 MHz), TMS as internal standard and H 3 PO 4 as external standard. MS: Agilent Q-TOF 6540 UHD or ThermoQuest Finnigan TSQ 7000. All manipulations were carried out under purified nitrogen. All solvents were dried and distilled before use according to standard procedures. (R)-Prophos and PPh(OMe) 2 were purchased from Wako Pure Chem. Ind. Ltd. (R Fe ,R C )/(S Fe ,R C )-(η 5 -Cyclopentadienyl)[propane-1,2-diylbis(diphenylphosphane-κP)[dimethoxy(phenyl)phosphane-κP]iron Eur. J. Inorg. Chem. 2016, 5405-5410 www.eurjic.org

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“…We had previously described the compression of the rotation angles of the face/edge/ trans ‐phenyls of the PPh 3 ligand in half‐sandwich complexes to narrow degree intervals, without recognizing the directionality, popping up in the best‐fit lines of Figure . For Ph face , the ‘reaction’ VIVTEZ→KEWSEK is shown at the bottom of Figure .…”

Section: Figurementioning

confidence: 99%

“…We had previously described the compression of the rotation angles of the face/edge/trans-phenylso ft he PPh 3 ligand in half-sandwich complexes to narrow degree intervals, without recognizing the directionality,p oppingu pi nt he best-fit lines of Figure 4. [7] For Ph face ,t he 'reaction' VIVTEZ!KEWSEK is showna tt he bottom of Figure 4. Going down from VIVTEZ to KEWSEK,P h face performsaclockwise rotation of t = 28.78.S imultaneously,t he PPh 3 ligand rotates in the counter-clockwise directionb y1 = 4.08.T his is not much;h owever,i th as to be kept in mind that PPh 3 rotationi ss trictly limited to narrow intervals and for the 'reaction' HAPSIA!GIBTUG the PPh 3 rotation amounts to 1 = 17.48.…”

mentioning

confidence: 99%

Trend‐Analysis of Solid‐State Structures: Low‐Energy Conformational ‘Reactions’ Involving Directed and Coupled Movements in Half‐Sandwich Compounds [CpFe(CO){C(=O)R}PPh₃]

Brunner

Tsuno

2018

ChemistryOpen

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Trends in solid‐state structures were used to identify preferred intramolecular movements in half‐sandwich compounds [CpFe(CO){C(=O)R}PPh3]. Three weak interactions were analyzed: 1) the CH/π donor–acceptor interaction of phenyl rings in the PPh3 ligand, 2) the PhPPh3 face‐on Cp stabilization, and 3) the hydrogen bond between the oxygen atom of the acyl group and an ortho‐C−H bond of one of the PPh3 phenyl rings. Clockwise and counter‐clockwise rotations established directed and coupled movements of the PPh3 ligand, the acyl group, and the phenyl rings within the PPh3 ligand.

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Solid-state conformations of compounds (arene)L2MP(C6H5)3 and (arene)LL'MP(C6H5)3

Cited by 26 publications

References 5 publications

PPh₃ Propeller Diastereomers: Bonding Motif Ph_PPh₃ Face-On π-Ar in Half-Sandwich Compounds [(π-Ar)LL′MPPh₃]

PPh₃ Propeller Diastereomers: Bonding Motif Ph_PPh₃ Face-On π-Ar in Half-Sandwich Compounds [(π-Ar)LL′MPPh₃]

Co‐Crystallization of Half‐Sandwich (R_M,R_C)/(S_M,R_C) Diastereomers in Single Crystals

Trend‐Analysis of Solid‐State Structures: Low‐Energy Conformational ‘Reactions’ Involving Directed and Coupled Movements in Half‐Sandwich Compounds [CpFe(CO){C(=O)R}PPh₃]

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Solid-state conformations of compounds (arene)L2MP(C6H5)3 and (arene)LL'MP(C6H5)3

Cited by 26 publications

References 5 publications

PPh3 Propeller Diastereomers: Bonding Motif PhPPh3 Face-On π-Ar in Half-Sandwich Compounds [(π-Ar)LL′MPPh3]

PPh3 Propeller Diastereomers: Bonding Motif PhPPh3 Face-On π-Ar in Half-Sandwich Compounds [(π-Ar)LL′MPPh3]

Co‐Crystallization of Half‐Sandwich (RM,RC)/(SM,RC) Diastereomers in Single Crystals

Trend‐Analysis of Solid‐State Structures: Low‐Energy Conformational ‘Reactions’ Involving Directed and Coupled Movements in Half‐Sandwich Compounds [CpFe(CO){C(=O)R}PPh3]

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PPh₃ Propeller Diastereomers: Bonding Motif Ph_PPh₃ Face-On π-Ar in Half-Sandwich Compounds [(π-Ar)LL′MPPh₃]

PPh₃ Propeller Diastereomers: Bonding Motif Ph_PPh₃ Face-On π-Ar in Half-Sandwich Compounds [(π-Ar)LL′MPPh₃]

Co‐Crystallization of Half‐Sandwich (R_M,R_C)/(S_M,R_C) Diastereomers in Single Crystals

Trend‐Analysis of Solid‐State Structures: Low‐Energy Conformational ‘Reactions’ Involving Directed and Coupled Movements in Half‐Sandwich Compounds [CpFe(CO){C(=O)R}PPh₃]