Preparation And Structure Of Phosphonium Ions With Intramolecular P ← N Coordination; Novel Diphosphonium Salts And Ionomer Containing Backbone Hypervalent Phosphorus

On the reaction of 4-substituted trimethyltin aromatics with perchlorylfluoride

“…3 is a reactive and rather instable compound [14] and was characterized as adduct with diethyl ether by 1 H NMR. Contrary to the results obtained with naphthalen-2-yl-lithium [8], no fluorinated product was formed even under varying reaction conditions in agreement with Schuetz et al [15].…”

Dative N→P/Si Interactions — A Historical Approach [1]

“…The exocyclic bonds emanating from them would be parallel so that this would also be the distance of peri-substituents provided that the two bonds are of equal length [1,[27][28][29][30][31]. This peri-distance, "PD", is sufficient to accommodate two hydrogen atoms (Σr(vdW H,H ) ϭ 240 pm [35]), but it is 2) The consistent and indiscriminate use of the symbol NǞSi/P and of the term dative bond (or its semantic equivalents such as intramolecular donor-acceptor or donating interaction [7,8,10,15]) in cases where short distances d(N···Si/P) indicate some sort of attractive interactions and TBP and octahedral geometries [22] are incontestable evidence of (covalent) hypercoordination as well as in the cases of very long distances d(N···Si/P) and of capped tetrahedral geometry leaves no doubt that in the latter category the terms interaction and coordination are not to be understood in a purely geometrical sense as in ionic crystals. This peri-distance, "PD", is sufficient to accommodate two hydrogen atoms (Σr(vdW H,H ) ϭ 240 pm [35]), but it is 2) The consistent and indiscriminate use of the symbol NǞSi/P and of the term dative bond (or its semantic equivalents such as intramolecular donor-acceptor or donating interaction [7,8,10,15]) in cases where short distances d(N···Si/P) indicate some sort of attractive interactions and TBP and octahedral geometries [22] are incontestable evidence of (covalent) hypercoordination as well as in the cases of very long distances d(N···Si/P) and of capped tetrahedral geometry leaves no doubt that in the latter category the terms interaction and coordination are not to be understood in a purely geometrical sense as in ionic crystals.…”

“…In peri-disubstituted naphthalenes, the energetic situation is so highly governed by the geometry and steric congestion that any attempt to 14) Another procedure to calculate % TBP character was proposed by Tamao et. 15) Application to various naphthalenes 1-X-8-Y-C 10 H 6 with d(X···Y) < Σr(vdW) would lead to the following formal degrees of hypercoordination (X, Y, involved atoms, degree): a) Me 2 N, (Ph)(DAN)(S)P, N/P 17%, b) Me 2 N, Me 2 N, N/N 18%, c) Me 2 N, [(Ph) 2 (Me)Si] 2 (Me)Si, N/Si 18%, d) Ph, Ph, C/C 20%, e) F, F, F/F 24%, f) Me, Me, C/C 25%, g) Me 2 P, Me 2 P, P/P 27/30%, h) Ph 2 P, Ph 2 P, P/P 29%, i) Me 2 N, P(C 12 H 8 ) 2 , N/P 30% [55], j) MeO, MeO, O/O 35%, k) Me 2 N, Ph 2 P, N/P 36/38% (r(vdW): Batsanov [85]; r(cov): Pauling [86]). [83].…”

“…An entirely novel type of hypercoordination was claimed to exist in which the basically tetrahedral coordination of tetracovalent P/Si is preserved rather than replaced by a trigonal-bipyramidal and octahedral geometry of "classical" penta-and hexacoordination, respectively 1) [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. An entirely novel type of hypercoordination was claimed to exist in which the basically tetrahedral coordination of tetracovalent P/Si is preserved rather than replaced by a trigonal-bipyramidal and octahedral geometry of "classical" penta-and hexacoordination, respectively 1) [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17].…”

C–H activation of diphenylphosphinoaryl-derivatives with dimethyltetrakis(trimethylphosphine)iron(II)

“…Literature methods were used in the preparation of trimethylsilylethyne and tert-butylethyne [24], 1-diphenylphosphinonaphthalene [25], benzyldiphenyl-phosphine [26], 2-diphenylphosphinotoluene [27], dimethyltetrakis(trimethyl-phosphine)eisen(II) [28]. Other chemicals were used as purchased.…”