2,2-Dimesityl-1-(2,4,6-tri-tert-butylphenyl)germaphosphene: the first stable compound with a germanium-phosphorus double bond

Escudié, J.; Couret, C.; Satgé, J.; Andrianarison, M.; Andriamizaka, Jean Dominique

doi:10.1021/ja00297a071

Cited by 76 publications

(27 citation statements)

References 2 publications

(6 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is consistent with a significant degree of multiple bond character in the GeÀP1 bond (IV, Scheme 1); for comparison, the GeÀP distance in [CH- 14] A relatively short GeÀP distance (2.291(4) ) is also observed in the two-coordinate phosphagermylene [2,6-(Tripp) 2 C 6 H 3 ]Ge[P(SiMe 3 ) 2 ] (4), although this compound contains a pyramidal phosphorus center and so does not possess significant GeÀP multiple bond character (Tripp = 2,4,6-iPr 3 C 6 H 2 ). [7d] The GeÀP1 distance in 2 is somewhat longer than the corresponding distances in previously reported phosphagermene compounds, although we note that these involve a Ge IV = P double bond; for example, the Ge À P distances in (Mes) 2 Ge = P(Mes*) (5) [15] and (tBu 2 MeSi) 2 Ge = P(Mes*) (6) [16] are 2.138(3) and 2.1748 (14) , respectively (Mes = 2,4,6-Me 3 C 6 H 2 , Mes* = 2,4,6-tBu 3 C 6 H 2 ). The P1-Ge-P2 angle of 107.40(4)8 is similar to the P-Ge-C angle (106.89 (5)8) …”

mentioning

confidence: 62%

Stabilization of a Diphosphagermylene through pπ–pπ Interactions with a Trigonal‐Planar Phosphorus Center

et al. 2014

View full text Add to dashboard Cite

N-Heterocyclic carbenes and their heavier homologues are, in part, stabilized by delocalization of the N lone pairs into the vacant p-orbital at carbon (or a heavier Group 14 element center). These interactions are usually absent in the corresponding P-substituted species, owing to the large barrier to planarization of phosphorus. However, judicious selection of the substituents at phosphorus has enabled the synthesis of a diphosphagermylene, [(Dipp)2P]2 Ge, in which one of the P centers is planar (Dipp=2,6-diisopropylphenyl). The planar nature of this P center and the correspondingly short P-Ge distance suggest a significant degree of P-Ge multiple bond character that is due to delocalization of the phosphorus lone pair into the vacant p-orbital at germanium. DFT calculations support this proposition and NBO and AIM analyses are consistent with a Ge-P bond order greater than unity.

show abstract

mentioning

confidence: 62%

Stabilization of a Diphosphagermylene through pπ–pπ Interactions with a Trigonal‐Planar Phosphorus Center

et al. 2014

View full text Add to dashboard Cite

show abstract

“…about atom Ru(2) in 3a, and two CO groups and a monodentate dppm ligand about atom Ru (2) in 3c. The coordination site occupied by atom P(3) of the dppm ligand is trans to the Ru(1)-Ru (2) bond.…”

Section: Resultsmentioning

confidence: 99%

“…2 The activation of phosphorus-containing ligands promoted by metal clusters is a typical example where the participation of adjacent metal centers seems to be required. Studies of the elementary steps involved in such transformations are important to our knowledge of "basic" cluster reactions.…”

Section: Introductionmentioning

confidence: 99%

Role of the reversible opening of a metal-metal bond in a cluster-assisted transformation of bis(diphenylphosphino)methane

Lugan¹,

Bonnet²,

Ibers³

1988

Organometallics

View full text Add to dashboard Cite

A reinvestigation of the reaction of Ru3(CO)~(~3-s3-P(C6H5)CH2P(C6H5)(C6H4)) (2) with carbon monoxide (Lugan, N.; Bonnet, J.-J.; Ibers, J. A. J. Am. Chem. SOC. 1985, 107, 4484-4491) under milder conditionsshows that a t room temperature 2 is in equilibrium with the adduct Ru~(CO)~~(CL~:~~-P(C~H~)CH~P-(C6H,)(C6H4)) (3a), in which one Ru-Ru bond has been broken. 3a has been isolated in 82% yield upon crystallization at -30 "C under a CO atmosphere. Similarly, 2 reacts at 0 "C with phosphines to afford compounds of general formula R U~( C O ) B L (~~-~~-P ( C B H~) C H~P ( C~H~) ( C~H~) ) (3b, L = P(C6H5)~; 3c, L = dppm). Addition of triphenylphosphine to compound 2 at 25 "C or warming a solution of 3a gives, among several compounds that have not been identified, the new dinuclear complex Ru~(CO)~(CL-?~-P(C~H~!-CH2P(C6H6)(C,H4)) (5). The nature of compounds 3a, 3b 312, and 5 has been established by spectroscopic means and for compound 3a, 3c, and 5 by X-ray diffraction methods. Crystal data: 3a, triclinic, Ct-PI, 2 = 2, a = 13.435 (2) A, b = 14.039 (2) A, c = 9.839 (2) A, a = 92.50 (l)", @ = 113.94 (l)", y = 92.86 (1)" ( t = -165 "C), final R(F) = 1.9%, NO = 5277, NV = 424; 3c, monoclinic, C&-P21/c, 2 = 4, a = 14.368 (2) A, b = 25.612 (2) A, c = 15.913 (2) A, @ = 108.09 (1)" (t = -150 "C), final R(F) = 6.8%, NO = 6301, NV = 412; 5, monoclinic, Ck-P21/c, Z = 4, a = 13.625 (3) A, b = 9.951 (2) A, c = 18.917 (4) A, @ = 97.46 (2)" (t = -155 "C), final R ( F ) = 4.8%, NO = 4404, NV = 316.

show abstract

“…[7d] The GeÀP1 distance in 2 is somewhat longer than the corresponding distances in previously reported phosphagermene compounds, although we note that these involve a Ge IV = P double bond; for example, the Ge À P distances in (Mes) 2 Ge = P(Mes*) (5) [15] and (tBu 2 MeSi) 2 Ge = P(Mes*) (6) [16] are 2.138(3) and 2.1748 (14) , respectively (Mes = 2,4,6-Me 3 C 6 H 2 , Mes* = 2,4,6-tBu 3 C 6 H 2 ). The P1-Ge-P2 angle of 107.40(4)8 is similar to the P-Ge-C angle (106.89 (5)8) …”

mentioning

confidence: 85%

“…Compounds with a planar phosphorus center involved in a Ge IV = P bond typically have downfield 31 P chemical shifts (for example, 175.4 (5), 416.3 (6) ppm), [15,16] while diphosphagermylenes with pyramidal phosphorus centers typically have 31 P chemical shifts close to those of the free phosphine. [5,6] We therefore assign the broad signals A and D in the lowtemperature solution-state spectrum (and the corresponding signals at 81.9 and À61.6 ppm in the solid-state NMR spectrum) to the planar and pyramidal phosphorus centers in 2, respectively.…”

Section: Inmentioning

confidence: 99%

Stabilization of a Diphosphagermylene through pπ–pπ Interactions with a Trigonal‐Planar Phosphorus Center

et al. 2014

View full text Add to dashboard Cite

N-Heterocyclic carbenes and their heavier homologues are, in part, stabilized by delocalization of the N lone pairs into the vacant p-orbital at carbon (or a heavier Group 14 element center). These interactions are usually absent in the corresponding P-substituted species, owing to the large barrier to planarization of phosphorus. However, judicious selection of the substituents at phosphorus has enabled the synthesis of a diphosphagermylene, [(Dipp) 2 P] 2 Ge, in which one of the P centers is planar (Dipp = 2,6-diisopropylphenyl). The planar nature of this P center and the correspondingly short PÀGe distance suggest a significant degree of PÀGe multiple bond character that is due to delocalization of the phosphorus lone pair into the vacant p-orbital at germanium. DFT calculations support this proposition and NBO and AIM analyses are consistent with a Ge À P bond order greater than unity.

show abstract

2,2-Dimesityl-1-(2,4,6-tri-tert-butylphenyl)germaphosphene: the first stable compound with a germanium-phosphorus double bond

Cited by 76 publications

References 2 publications

Stabilization of a Diphosphagermylene through pπ–pπ Interactions with a Trigonal‐Planar Phosphorus Center

Stabilization of a Diphosphagermylene through pπ–pπ Interactions with a Trigonal‐Planar Phosphorus Center

Role of the reversible opening of a metal-metal bond in a cluster-assisted transformation of bis(diphenylphosphino)methane

Stabilization of a Diphosphagermylene through pπ–pπ Interactions with a Trigonal‐Planar Phosphorus Center

Contact Info

Product

Resources

About