Abstract:03-Phosphazene des Typs >N-P(X)=N-, X = z. B. NR, S, Se, weisen vielseitige Ligandeneigenschaften auf'). Im Gegensatz zu den Amino(imino)chalkogenphosphoranen3~ (X = S , Se) konnen Aminobis(imino)phosphorane (X = NR) bislang nicht durch deren Umsetzung mit geeigneten Ubergangsmetall-Komplexfragmenten zur side-on-Koordination einer ihrer Ylid-Funktionen (Doppelylide) herangezogen werden.
q*-Koordination von a3-PhosphazenenAusgehend von [(dppe)Ni(q2-R2N-P = NR)] (1 a)4), R = SiMe,, kann dessen side-on-koordinier… Show more
“…Heavy main-group elements are known for their ability to support small bond angles, but the N−Tl−S bond angle (63.44(6)°) is small even for thallium. The thallium−nitrogen (2.534(3) Å) and thallium−sulfur (2.8861(9) Å) bonds are similar to those in related compounds. − Thus for example, the four Tl−N bonds in the heterocubic [P(μ-N t Bu) 2 P( t BuN-κ N 3 Tl) 2 ] range from 2.559(3) to 2.587(3) Å, while the Tl−S bonds in thallium dithiocarbamate dimers of the formula {[(C 3 H 7 ) 2 NCS 2 -κ S 2 ]Tl]} 2 , due to the higher coordination number (4), vary from 2.88(1) to 3.12(1) Å. , 3 Solid-state structure of 7 (35% probability thermal ellipsoids). …”
Section: Resultsmentioning
confidence: 90%
“…The thallium-nitrogen (2.534(3) Å) and thallium-sulfur (2.8861(9) Å) bonds are similar to those in related compounds. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49] Thus for example, the four Tl-N bonds in the heterocubic [P(µ-N t Bu) 2 P( t BuN-κN 3 Tl) 2 ] range from 2.559(3) to 2.587(3) Å, 32 while the Tl-S bonds in thallium dithiocarbamate dimers of the formula {[(C 3 H 7 ) 2 NCS 2 -κS 2 ]Tl]} 2 , due to the higher coordination number (4), vary from 2.88(1) to 3.12(1) Å. 33,34 The low dimensionality of 7 is surprising, because, as the disubstituted zinc compounds 11-13 show (see below), the ligand is not particularly bulky and one might, therefore, have expected stronger intermolecular interactions, possibly even between thallium atoms.…”
The P-anilino-P-chalcogeno(imino)diazasilaphosphetidines [Me(2)Si(mu-N(t)Bu)(2)P=E(NHPh)] (E = O (3), S (4), Se (5), N-p-tolyl (6)) were synthesized by oxidizing the P-anilinodiazasilaphosphetidine [Me(2)Si(N(t)Bu)(2)P(NHPh)] (2) with cumene hydroperoxide, sulfur, selenium, and p-tolyl azide, respectively. The lithium salt of 4 reacted with thallium monochloride to produce ([Me(2)Si(mu-N(t)Bu)(2)P=S(NPh)-kappaN-kappaS]Tl)(7), which features a two-coordinate thallium atom. Treatment of 4-6 with AlMe(3) gave the monoligand dimethylaluminum complexes ([Me(2)Si(mu-N(t)Bu)(2)P=E(NPh)-kappaN-kappaE]AlMe(2)) (E = S (8), Se (9), N-p-tolyl (10)), respectively. In these complexes the aluminum atom is tetrahedrally coordinated by one chelating ligand and two methyl groups, as a single-crystal X-ray analysis of 8 showed. A 2 equiv amount of 4-6 reacted with diethylzinc to produce the homoleptic diligand complexes ([Me(2)Si(mu-N(t)Bu)(2)P=E(NPh)-kappaN-kappaE](2)Zn)(E = S (11), Se (12), N-p-tolyl (13)). A crystal-structure analysis of 11 revealed a linear tetraspirocycle with a tetrahedrally coordinated, central zinc atom.
“…Heavy main-group elements are known for their ability to support small bond angles, but the N−Tl−S bond angle (63.44(6)°) is small even for thallium. The thallium−nitrogen (2.534(3) Å) and thallium−sulfur (2.8861(9) Å) bonds are similar to those in related compounds. − Thus for example, the four Tl−N bonds in the heterocubic [P(μ-N t Bu) 2 P( t BuN-κ N 3 Tl) 2 ] range from 2.559(3) to 2.587(3) Å, while the Tl−S bonds in thallium dithiocarbamate dimers of the formula {[(C 3 H 7 ) 2 NCS 2 -κ S 2 ]Tl]} 2 , due to the higher coordination number (4), vary from 2.88(1) to 3.12(1) Å. , 3 Solid-state structure of 7 (35% probability thermal ellipsoids). …”
Section: Resultsmentioning
confidence: 90%
“…The thallium-nitrogen (2.534(3) Å) and thallium-sulfur (2.8861(9) Å) bonds are similar to those in related compounds. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49] Thus for example, the four Tl-N bonds in the heterocubic [P(µ-N t Bu) 2 P( t BuN-κN 3 Tl) 2 ] range from 2.559(3) to 2.587(3) Å, 32 while the Tl-S bonds in thallium dithiocarbamate dimers of the formula {[(C 3 H 7 ) 2 NCS 2 -κS 2 ]Tl]} 2 , due to the higher coordination number (4), vary from 2.88(1) to 3.12(1) Å. 33,34 The low dimensionality of 7 is surprising, because, as the disubstituted zinc compounds 11-13 show (see below), the ligand is not particularly bulky and one might, therefore, have expected stronger intermolecular interactions, possibly even between thallium atoms.…”
The P-anilino-P-chalcogeno(imino)diazasilaphosphetidines [Me(2)Si(mu-N(t)Bu)(2)P=E(NHPh)] (E = O (3), S (4), Se (5), N-p-tolyl (6)) were synthesized by oxidizing the P-anilinodiazasilaphosphetidine [Me(2)Si(N(t)Bu)(2)P(NHPh)] (2) with cumene hydroperoxide, sulfur, selenium, and p-tolyl azide, respectively. The lithium salt of 4 reacted with thallium monochloride to produce ([Me(2)Si(mu-N(t)Bu)(2)P=S(NPh)-kappaN-kappaS]Tl)(7), which features a two-coordinate thallium atom. Treatment of 4-6 with AlMe(3) gave the monoligand dimethylaluminum complexes ([Me(2)Si(mu-N(t)Bu)(2)P=E(NPh)-kappaN-kappaE]AlMe(2)) (E = S (8), Se (9), N-p-tolyl (10)), respectively. In these complexes the aluminum atom is tetrahedrally coordinated by one chelating ligand and two methyl groups, as a single-crystal X-ray analysis of 8 showed. A 2 equiv amount of 4-6 reacted with diethylzinc to produce the homoleptic diligand complexes ([Me(2)Si(mu-N(t)Bu)(2)P=E(NPh)-kappaN-kappaE](2)Zn)(E = S (11), Se (12), N-p-tolyl (13)). A crystal-structure analysis of 11 revealed a linear tetraspirocycle with a tetrahedrally coordinated, central zinc atom.
“…Two Ni°c omplexes 50a,b have been reported where the ligand Me3SiN=PN(SiMe3)2 has been formulated as irbonded. 16,17 In analogy to other ligands with heteropolar double bonds, e.g. hexafluoroacetone192 and from the X-ray structure data of 50a (Ni-P «= 223 pm, Ni-N « 191 pm, and P-N «= 165 pm),16 a three-membered ring as depicted with Ni2+ seems to be more likely.…”
Section: A Metal Bound To One Element Other Than Nitrogenmentioning
The metaphosphate anion has attracted steady interest since 1955 [1] in connection with wide applications in phosphorylation reactions.[2] It has relevance in biochemistry in particular with respect to ATP hydrolysis.[3] However, despite considerable efforts, monomeric metaphosphates and other dioxophosphoranes are only known as transient species in solution and their existence can be inferred from trapping experiments. [2][3][4] Their high reactivity arises from the powerful electrophilic character at the phosphorus center. Several approaches have been tested to stabilize these highly reactive species. Kinetic stabilization by steric protection [5] proved to be ineffective for dioxophosphorane and led to products that resulted from the insertion of the PO 2 moiety in a neighboring group.[6] The electrophilicity and the tendency to expand the valence shell were exploited for their stabilization as Lewis salts. This strategy allowed only spectroscopic characterization by 31 P NMR in a few cases. [7] Thus, the chemistry of dioxophosphorane suffers from a paucity of information and new approaches to stabilize and enable deeper investigation are highly desirable. This work describes the first isolation and full characterization, including X-ray structural analysis, of stabilized metaphosphonate.We have developed a novel and successful route to ruthenium-stabilized monomeric metaphosphonate by oxidation of a nucleophilic terminal phosphinidene complex of ruthenium. As recently described by Lammerstma and coworkers, the terminal phosphinidene ruthenium complexes [(h 6 -p-cymene)Ru(PR 3 )(PMes*)] (3 a: R = Cy, 3 b: R = Ph [8] ) are formed as dark green solids by the reaction of the primary phosphane complex [(h 6 -p-cymene)RuCl 2 (PH 2 Mes*)](1; pcymene = 4-methyl-iso-propylbenzene; Mes* = 2,4,6-tri-tertbutylphenyl) with two equivalents of 1,8-diazabicyclo[5-4-0]undec-7-ene (DBU) in the presence of PR 3 as a stabilizing ligand (R = Ph, Cy).[8] Alternatively, treatment of [(h 6 -pcymene)RuCl 2 (PR 3 )] (2 a: R = Cy, 2 b: R = Ph) and PH 2 Mes* with DBU affords 3 in high yields (Scheme 1).
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