Unsaturated germanium and phosphorus compounds: reactions of germaphosphenes with .alpha.-ethylene aldehydes and ketones

Ranaivonjatovo, H.; Escudié, J.; Couret, C.; Declercq, Jean‐Paul; Dubourg, A.; Satgé, J.

doi:10.1021/om00029a027

Cited by 17 publications

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“…In many cases, the origins for low barriers to inversion at phosphorus in specific compounds are attributed to various sources that include steric effects, substituent electronegativities, and conjugation with a transition metal. 26,27 The first observation of inversion at phosphorus in a polycyclophosphane was reported by Baudler et al for the compounds P 9 R 3 (R ) Et, t-Bu). The inversion barrier (E a ) for P 9 -t-Bu 3 was determined to be 18.5 kcal/mol, which is in the range of inversion barriers for open-chain organophosphanes with P-P bonds in their molecular skeletons.…”

Section: Discussionmentioning

confidence: 99%

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Rapid Inversion at Phosphorus in the [η⁴-(C₆H₁₁)₃SnP₇W(CO)₃]²^-and [(en)(CO)₃W(η¹,η⁴-P₇)M(CO)₃]³^-Ions Where M = Cr, W

et al. 1997

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Ethylenediamine (en) solutions of [eta(4)-P(7)M(CO)(3)](3)(-) ions [M = Cr (1a), W (1b)] react with (mesitylene)W(CO)(3) to form the bimetallic complexes [(en)(CO)(3)W(eta(1),eta(4)-P(7))M(CO)(3)](3)(-) where M = Cr (3a), W (3b) in good yield. Compound 3b can be prepared directly from P(7)(3)(-) and 2 equiv of (mesitylene)W(CO)(3). Compound 3a reacts with 1 equiv of P(7)(3)(-) to form 1a and 1b. En solutions of 1b react with 1 equiv of (C(6)H(11))(3)SnCl to give [eta(4)-(C(6)H(11))(3)SnP(7)W(CO)(3)](2)(-) (4) in good crystalline yield as the [K(2,2,2-crypt)](+) salt. The X-ray structure of the [K(2,2,2-crypt)](+) salt 3b revealed a norbornadiene-like P(7) cage bound eta(4) to the W(CO)(3) fragment (cf. [eta(4)-P(7)W(CO)(3)](3)(-)) and eta(1) to the (en)(CO)(3)W fragment via the long W(2)-P(1) bond of 2.643(3) Å. The structure of 4 is similar, with a (C(6)H(11))(3)Sn(+) group attached to the P(1) atom of the [eta(4)-P(7)W(CO)(3)](3)(-) complex. The coordination geometry at P(1) is distinctly pyramidal in both compounds, which leaves the ions with no crystallographic symmetry. For complexes 3a and 3b, two fluxional processes are rapid on the NMR time scale at -50 degrees C (202 MHz) that give the P(7) cages virtual C(2)(v)() symmetry in solution and AA'A"A"'MM"X spin systems. These processes are (1) a wagging of the four P atoms bound to the M(CO)(3) units and (2) rapid inversion at P(1). For 4, inversion at phosphorus becomes slow on the NMR time scale at low temperature (-50 degrees C, 83 MHz) with DeltaG() = 13 kcal/mol. Crystallographic data are as follows. [K(2,2,2-crypt)](3)3b.en: triclinic, P&onemacr;, a = 14.396(4) Å, b = 17.543(3) Å, c = 20.518(2) Å, alpha = 82.419(11) degrees, beta = 76.830(14) degrees, gamma = 69.16(2) degrees, V = 4708(2) Å(3), Z = 2, R(F) = 5.52%, R(w)(F(2)) = 14.31%. [K(2,2,2-crypt)](2)4: triclinic, P&onemacr;, a = 12.247(2) Å, b = 15.1909(14) Å, c = 21.292(3) Å, alpha = 97.374(10) degrees, beta = 93.273(13) degrees, gamma = 111.217(9) degrees, V = 3639.8(8) Å(3), Z = 2, R(F) = 10.50%, R(w)(F(2)) = 20.21%.

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Section: Discussionmentioning

confidence: 99%

“…19 kcal/mol. In many cases, the origins for low barriers to inversion at phosphorus in specific compounds are attributed to various sources that include steric effects, substituent electronegativities, and conjugation with a transition metal. , …”

Section: Discussionmentioning

confidence: 99%

Rapid Inversion at Phosphorus in the [η⁴-(C₆H₁₁)₃SnP₇W(CO)₃]²^-and [(en)(CO)₃W(η¹,η⁴-P₇)M(CO)₃]³^-Ions Where M = Cr, W

et al. 1997

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“…Though multiple bonding plays a fundamental role in the chemistry of the second-row elements (such as carbon, nitrogen, and oxygen), complexes that exhibit multiple bonding to the heavier congeners of these elements are much less common. − For instance, even though much effort has been directed toward the study of multiple bonding to germanium, monomeric germaphosphenes with GeP double bonds are kinetically unstable due to the lack of stabilization by bulky groups. They have been frequently postulated as intermediates, mostly on the evidence of trapping experiments. , Only in the last 10 years have sufficiently stable germaphosphenes been stabilized to allow their analysis in the solid state and in solution. − …”

Section: Introductionmentioning

confidence: 99%

A Theoretical Study of Substituent Effects on Germanium−Phosphorus Triple Bonds

Lai

Chu

2001

J. Phys. Chem. A

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To extend our knowledge of the germanium-phosphorus triple bond, the isomerization reactions of singlet XGeP (i.e., XGetP f TS f GedPX; X ) H, Li, BeH, BH 2 , CH 3 , SiH 3 , NH 2 , PH 2 , OH, SH, F, and Cl) were investigated using B3LYP and CCSD(T) calculations. It is found that electronegative and π-electrondonating substituents (X) can stabilize the XGetP triply bonded species in a kinetic sense, although germanium is less reluctant to form GedP doubly bonded than GetP triply bonded compounds.

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Phosphine‐Stabilized Pnictinidenes

Raiser

Eichele

Schubert

et al. 2021

Chemistry A European J

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The reaction of the intramolecular germylenephosphine Lewis pair (o-PPh 2 )C 6 H 4 GeAr* (1) with Group 15 element trichlorides ECl 3 (E=P, As, Sb) was investigated. After oxidative addition, the resulting compounds (o-PPh 2 )C 6 H 4 (Ar*) Ge(Cl)ECl 2 (2: E=P, 3: E=As, 4: E=Sb) were reduced by using sodium metal or LiHBEt 3 . The molecular structures of the phosphine-stabilized phosphinidene (o-PPh 2 )C 6 H 4 (Ar*)Ge(Cl)P ( 5), arsinidene (o-PPh 2 )C 6 H 4 (Ar*)Ge(Cl)As ( 6) and stibinidene (o-PPh 2 )C 6 H 4 (Ar*)Ge(Cl)Sb ( 7) are presented; they feature a two-coordinate low-valent Group 15 element. After chloride abstraction, a cyclic germaphosphene [(o-PPh 2 )C 6 H 4 (Ar*)GeP] [B(C 6 H 3 (CF 3 ) 2 ) 4 ] (8) was isolated. The 31 P NMR data of the germaphosphene were compared with literature examples and analyzed by quantum chemical calculations. The phosphinidene was treated with [iBu 2 AlH] 2 , and the product of an AlÀ H addition to the low-valent phosphorus atom (o-PPh 2 ) C 6 H 4 (Ar*)Ge(H)P(H)Al(C 4 H 9 ) 2 ( 9) was characterized.

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Unsaturated germanium and phosphorus compounds: reactions of germaphosphenes with .alpha.-ethylene aldehydes and ketones

Cited by 17 publications

References 1 publication

Rapid Inversion at Phosphorus in the [η⁴-(C₆H₁₁)₃SnP₇W(CO)₃]²^-and [(en)(CO)₃W(η¹,η⁴-P₇)M(CO)₃]³^-Ions Where M = Cr, W

Rapid Inversion at Phosphorus in the [η⁴-(C₆H₁₁)₃SnP₇W(CO)₃]²^-and [(en)(CO)₃W(η¹,η⁴-P₇)M(CO)₃]³^-Ions Where M = Cr, W

A Theoretical Study of Substituent Effects on Germanium−Phosphorus Triple Bonds

Phosphine‐Stabilized Pnictinidenes

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Unsaturated germanium and phosphorus compounds: reactions of germaphosphenes with .alpha.-ethylene aldehydes and ketones

Cited by 17 publications

References 1 publication

Rapid Inversion at Phosphorus in the [η4-(C6H11)3SnP7W(CO)3]2-and [(en)(CO)3W(η1,η4-P7)M(CO)3]3-Ions Where M = Cr, W

Rapid Inversion at Phosphorus in the [η4-(C6H11)3SnP7W(CO)3]2-and [(en)(CO)3W(η1,η4-P7)M(CO)3]3-Ions Where M = Cr, W

A Theoretical Study of Substituent Effects on Germanium−Phosphorus Triple Bonds

Phosphine‐Stabilized Pnictinidenes

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Rapid Inversion at Phosphorus in the [η⁴-(C₆H₁₁)₃SnP₇W(CO)₃]²^-and [(en)(CO)₃W(η¹,η⁴-P₇)M(CO)₃]³^-Ions Where M = Cr, W

Rapid Inversion at Phosphorus in the [η⁴-(C₆H₁₁)₃SnP₇W(CO)₃]²^-and [(en)(CO)₃W(η¹,η⁴-P₇)M(CO)₃]³^-Ions Where M = Cr, W