Dibridgehead Diphosphines that Turn Themselves Inside Out

Stollenz, Michael; Barbasiewicz, Michał; Nawara‐Hultzsch, Agnieszka J.; Fiedler, Tobias; Laddusaw, Ryan M.; Bhuvanesh, Nattamai; Gladysz, J. A.

doi:10.1002/anie.201100893

Cited by 49 publications

(46 citation statements)

References 31 publications

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“…Alternatively, the crude product was treated with BH 3 ⋅S(CH 3 ) 2 . This gave the previously reported30 bis(borane) adduct 19 ⋅(BH 3 ) 2 as a white solid in 78 % overall yield. Single crystals were obtained, and the crystal structure determined (Experimental Section).…”

Section: Resultssupporting

confidence: 69%

“…In the course of exploring the above substitution chemistry, unexpected demetalations that liberated the diphosphine ligands were discovered. Although these represent the start of major ongoing investigations involving the demetalation mechanism and diphosphine properties,30, 31 certain results bear upon key synthetic or structural issues above. Hence, selected observations are presented here.…”

Section: Resultsmentioning

confidence: 99%

“…Workup of a comparable preparative reaction gave 18 as a moderately air‐sensitive white powder in 91 % yield. Based upon the mass spectrum, microanalysis, and chemistry described elsewhere,30, 31 this was assigned as the dibridgehead diphosphine corresponding to the stator of trans ‐ 4 c .…”

Section: Resultsmentioning

confidence: 99%

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Gyroscope‐Like Molecules Consisting of PdX₂/PtX₂ Rotators within Three‐Spoke Dibridgehead Diphosphine Stators: Syntheses, Substitution Reactions, Structures, and Dynamic Properties

Nawara‐Hultzsch

Stollenz

Barbasiewicz

et al. 2014

Chemistry A European J

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Threefold intramolecular ring-closing metatheses of trans-[MCl2(P{(CH2)(m)CH=CH2}3)2] are effected with Grubbs' catalyst. Following hydrogenation catalyzed by [RhCl(PPh3)3], the title complexes trans-[MCl2(P((CH2)n)3P)] (n=2m+2; M/n=Pt/14, 4 c; Pt/16, 4 d; Pt/18, 4 e; Pd/14, 5 c; Pd/18, 5 e) and sometimes isomers partly derived from intraligand metathesis, trans-[MCl2{P(CH2)n(CH2)n}P(CH2)n)] (4'c-e, 5'e), are isolated. These react with LiBr, NaI, and KCN to give the corresponding MBr2, MI2, and M(CN)2 species (58-99%). (13)C NMR data show that the MX2 moieties rapidly rotate within the diphosphine cage on the NMR timescale, even at -120 °C. The reaction of 4 c and KSCN gives separable Pt(NCS)2 and Pt(NCS)(SCN) adducts (13 c, 28%; 14 c, 20%), and those of 4 c,e and Ph2Zn give PtPh2 species (15 c, 61%; 15 e, 90%). (13)C NMR spectra of 13 c-15 c show two sets of CH2 signals (ca. 2:1 intensity ratios), indicating that MX2 rotation is no longer rapid. Reactions of 4 c or 4'c and excess NaC≡CH afford the free diphosphines P{(CH2)14}3P (91%) and (CH2)14P(CH2)14P(CH2)14 (90%). The latter has been crystallographically characterized as a bis(BH3) adduct. The crystal structures of eight complexes with P(CH2)14P linkages (PtCl2, PtBr2, PtI2, Pt(NCS)2, PtPh2, PdCl2, PdBr2, PdI2) and 15 e have been determined, and intramolecular distances analyzed with respect to MX2 rotation. The conformations of the (CH2)14 moieties and features of the crystal lattices are also discussed.

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Section: Resultssupporting

confidence: 69%

Section: Resultsmentioning

confidence: 99%

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Gyroscope‐Like Molecules Consisting of PdX₂/PtX₂ Rotators within Three‐Spoke Dibridgehead Diphosphine Stators: Syntheses, Substitution Reactions, Structures, and Dynamic Properties

Nawara‐Hultzsch

Stollenz

Barbasiewicz

et al. 2014

Chemistry A European J

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“…The crystal structure of the bis(BH 3 ) adduct of the free diphosphine ligand has been described elsewhere. 30 The molecular structures of the gyroscope like dibromide complex 7b and its longer chain homolog 7c (nineteen and twentyone membered macrocycles) are given in Fig. 7 and 8.…”

Section: Figmentioning

confidence: 99%

Gyroscope like molecules consisting of trigonal or square planar osmium rotators within three-spoked dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties

et al. 2016

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aReactions of (NH 4 ) 2 OsX 6 (X = Cl, Br) with CO and the phosphines P((CH 2 ) m CHvCH 2 ) 3 (m = 6, a; 7, b; 8, c) give cis,cis,trans-Os(CO) 2 (X) 2 (P((CH 2 ) m CHvCH 2 ) 3 ) 2 (46-73%). These are treated with Grubbs' catalyst (7 mol%, 0.0010 M, C 6 H 5 Cl). Subsequent hydrogenations (PtO 2 ) yield the gyroscope like complexes cis,cis,trans-Os(CO) 2 (X) 2 (P((CH 2 ) n ) 3 P) (n = 2m + 2; X = Cl, 6a-c; Br, 7a-c; 5-31%) and the isomers cis,cis,trans-Os(CO) 2 (X) 2 (P(CH 2 ) n−1 CH 2 )((CH 2 ) n )(P(CH 2 ) n−1 CH 2 ) (X = Cl, 6'a-c; Br, 7'a-c; 12-51%) derived from a combination of interligand and intraligand metatheses. Reductions of 6a,c, 6'b, and 7'b with C 8 K under CO atmospheres afford trans-Os(CO) 3 (P((CH 2 ) n ) 3 P) (9a,c, 79-82%) and trans-

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“…[19][20][21] The conversion of (R a ,R,S P )-1 h to (R a ,R,R P )-1 h was monitored by 1 H NMR spectroscopy in [D 7 ]DMF over temperatures ranging from 80 to 100 8C and provided a means of evaluating DG°, DH°, and DS°by applying the linear form of the Eyring equation. An excellent correlation was obtained for the plot of ln(k/T) as a function of 1/T (Figure 4; see the Supporting Information for additional details).…”

Section: Resultsmentioning

confidence: 99%

Highly Modular C₁‐Symmetric Chiral (P,N) Ligands with a Stereolabile P Center: Experimental and Theoretical Studies

Humbert

Larionov

Mantilli

et al. 2013

Chemistry A European J

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An improved synthesis of a novel class of bidentate (P,N) ligands is presented, the structures of which are characterized by three distinct elements of chirality. The stereoselective installation of the elements of central chirality (at the benzylic carbon and the phosphorus atom) depends on the size of the phosphorus substituent. Thermal inversion of the phosphorus center has been studied experimentally and further correlated by DFT calculations. The potential of these ligands and the role of the phosphorus atom in the asymmetric α-arylation of aldehydes (Pd) and hydrogenation of allylic alcohols (Ir) have also been investigated.

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Dibridgehead Diphosphines that Turn Themselves Inside Out

Cited by 49 publications

References 31 publications

Gyroscope‐Like Molecules Consisting of PdX₂/PtX₂ Rotators within Three‐Spoke Dibridgehead Diphosphine Stators: Syntheses, Substitution Reactions, Structures, and Dynamic Properties

Gyroscope‐Like Molecules Consisting of PdX₂/PtX₂ Rotators within Three‐Spoke Dibridgehead Diphosphine Stators: Syntheses, Substitution Reactions, Structures, and Dynamic Properties

Gyroscope like molecules consisting of trigonal or square planar osmium rotators within three-spoked dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties

Highly Modular C₁‐Symmetric Chiral (P,N) Ligands with a Stereolabile P Center: Experimental and Theoretical Studies

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Dibridgehead Diphosphines that Turn Themselves Inside Out

Cited by 49 publications

References 31 publications

Gyroscope‐Like Molecules Consisting of PdX2/PtX2 Rotators within Three‐Spoke Dibridgehead Diphosphine Stators: Syntheses, Substitution Reactions, Structures, and Dynamic Properties

Gyroscope‐Like Molecules Consisting of PdX2/PtX2 Rotators within Three‐Spoke Dibridgehead Diphosphine Stators: Syntheses, Substitution Reactions, Structures, and Dynamic Properties

Gyroscope like molecules consisting of trigonal or square planar osmium rotators within three-spoked dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties

Highly Modular C1‐Symmetric Chiral (P,N) Ligands with a Stereolabile P Center: Experimental and Theoretical Studies

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Gyroscope‐Like Molecules Consisting of PdX₂/PtX₂ Rotators within Three‐Spoke Dibridgehead Diphosphine Stators: Syntheses, Substitution Reactions, Structures, and Dynamic Properties

Gyroscope‐Like Molecules Consisting of PdX₂/PtX₂ Rotators within Three‐Spoke Dibridgehead Diphosphine Stators: Syntheses, Substitution Reactions, Structures, and Dynamic Properties

Highly Modular C₁‐Symmetric Chiral (P,N) Ligands with a Stereolabile P Center: Experimental and Theoretical Studies