Steric and Electronic Influences of Buchwald-Type Alkyl-JohnPhos Ligands

Kendall, Alexander J.; Zakharov, Lev N.; Tyler, David R.

doi:10.1021/acs.inorgchem.5b02996

Cited by 44 publications

(50 citation statements)

References 48 publications

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“…50° rotation of the ‐PMe 2 half around the P−C ipso bond to make one of the P−Me bonds almost coplanar with the Ar′ central ring, and opening of the P‐C ipso ‐C ortho bond angle of the PMe 2 unit and the closer side ring, partially relieves steric tension making conformation B somewhat more favourable than A . Experimentally, this is the molecular geometry ascertained for PMe 2 Ar

^{Xyl_{2}}

( L12 ) and PMe 2 Ar

^{Dipp_{2}}

( L14 ), as well as for the previously reported PMe 2 Ar

^{Mes_{2}}

( L13 ), P(C≡CH) 2 Ar

^{Mes_{2}}

, P(CH 2 CH=CH 2 ) 2 Ar

^{Dipp_{2}}

and the Buchwald‐type biaryl phosphine Methyl‐JohnPhos …”

Section: Resultssupporting

confidence: 80%

“…A recent study based on trans ‐PdCl 2 (PR 3 ) 2 complexes provided S4′ values for Buchwald‐type dialkylbiaryl phosphines, PR 2 Ar Ph , of ca. 28° (R=Me), 29.3° (Et), 29.8° (Ph) and 16.9 ( c ‐C 6 H 11 ) . Corresponding parameters for PMe 3 , PMe 2 Ph and P t Bu 2 Ph in these complexes were 35.3, 32.8 and 18.4°, respectively.…”

Section: Resultsmentioning

confidence: 80%

“…Moreover, attempts to synthesize Ni(CO) 3 (P( c ‐C 6 H 11 ) 2 Ar) complexes of Buchwald‐type biaryl (Ar) phosphines proved unsuccessful, because the ligands appeared to be too sterically demanding to stabilize such complexes . Recently, the steric and electronic properties of another series of dialkylbiaryl phosphines, PR 2 Ar Ph , were investigated using IR and X‐ray data collected for a diversity of Cr 0 , Pd 0 and Pd II compounds . We found that the target Ni 0 ‐CO‐PR 2 Ar′ complexes could be accessed with comparable reaction outcomes either by treatment of Ni(CO) 4 with PR 2 Ar′ or by carbonylation of 1:1 mixtures of Ni(cod) 2 and PR 2 Ar′ (cod=1,5‐cyclooctadiene).…”

Section: Resultsmentioning

confidence: 99%

“…[23][24][25][26][27][28] The objective of the present work was the description of a series of PR 2 Ar' molecules selected in accordance with the following criteria. Firstly,b esides someP Me 2 -containing phosphines, [28,29] we set out to prepare PR 2 Ar' phosphines of the branched andc yclic alkyl groups iPr and c-C 6 H 11, respectively, which are phosphine substituents extensively employed in organometallic chemistry and catalysis. The new terphenylp hosphines find applications in efficient Pd-catalyzeda mination reactions and Cu-promoted cycloaddition of azides and alkynes.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structure and Nickel Carbonyl Complexes of Dialkylterphenyl Phosphines

Marín

Moreno

Navarro-Gilabert

et al. 2018

Chemistry A European J

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The experimental and computational characterization of a series of dialkylterphenyl phosphines, PR2Ar′ is described. The new P‐donors comprise five compounds of general formula PR2ArDtbp2 (R=Me, Et, iPr, c‐C5H9 and c‐C6H11); ArDtbp2 = 2,6‐C6H3‐(3,5‐C6H3‐(CMe3)2)2), and another five PR2Ar′ phosphines containing the bulky alkyl groups iPr, c‐C5H9 or c‐C6H11, in combination with Ar′=ArXyl2 , ArXyl'2 , or ArPh2 (L1–L10). Steric and electronic parameters have been determined computationally and from IR and X‐ray data obtained for the phosphines and for some derivatives, including tricarbonyl and dicarbonyl nickel complexes, Ni(CO)3(PR2Ar′) and Ni(CO)2(PR2Ar′). In the solid state, the free phosphines PR2Ar′ adopt one of the three possible structures formally related by rotation around the Cipso−P bond. Details on their relative energies and on the influence of the free phosphine structure on its coordination chemistry towards Ni(CO)n (n = 2, 3) fragments has been obtained by experimental and computational methods.

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^{Xyl_{2}}

( L12 ) and PMe 2 Ar

^{Dipp_{2}}

( L14 ), as well as for the previously reported PMe 2 Ar

^{Mes_{2}}

( L13 ), P(C≡CH) 2 Ar

^{Mes_{2}}

, P(CH 2 CH=CH 2 ) 2 Ar

^{Dipp_{2}}

and the Buchwald‐type biaryl phosphine Methyl‐JohnPhos …”

Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 80%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis, Structure and Nickel Carbonyl Complexes of Dialkylterphenyl Phosphines

Marín

Moreno

Navarro-Gilabert

et al. 2018

Chemistry A European J

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“…It is noteworthy that this 2:1 trigonal gold(I) structure is similar to crystal structures reported for [(Ph 3 P) 2 Au (I) Cl] [16] and [(Ph 3 P) 2 Au (I) (SCN)]. [17] Furthermore a linear cationic gold(I) chloride complex [(Ph 3 P) 2 Au + ][Cl -] bearing two triphenyl phosphine ligands with a fully dissociated chloride counterion also been reported. [15b] Therefore, the crystal structure of 12 is included for completeness.…”

Section: Gold(i) Chloride Complex Synthesis and Structural Analysissupporting

confidence: 82%

Balancing Bulkiness in Gold(I) Phosphino‐triazole Catalysis

et al. 2019

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The syntheses of a series of 1‐phenyl‐5‐phosphino 1,2,3‐triazoles are disclosed, within which, the phosphorus atom (at the 5‐position of a triazole) is appended by one, two or three triazole motifs, and the valency of the phosphorus(III) atom is completed by two, one or zero ancillary (phenyl or cyclohexyl) groups respectively. This series of phosphines was compared with tricyclohexylphosphine and triphenylphosphine to study the effect of increasing the number of triazoles appended to the central phosphorus atom from zero to three triazoles. Gold(I) chloride complexes of the synthesised ligands were prepared and analysed by techniques including single‐crystal X‐ray diffraction structure determination. Gold(I) complexes were also prepared from 1‐(2,6‐dimethoxy)‐phenyl‐5‐dicyclohexyl‐phosphino 1,2,3‐triazole and 1‐(2,6‐dimethoxy)‐phenyl‐5‐diphenyl‐phosphino 1,2,3‐triazole ligands. The crystal structures thus obtained were examined using the SambVca (2.0) web tool and percentage buried volumes determined. The effectiveness of these gold(I) chloride complexes to serve as precatalysts for alkyne hydration were assessed. Furthermore, the regioselectivity of hydration of but‐1‐yne‐1,4‐diyldibenzene was probed.

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