The first bidentate phosphanylborohydride: Synthesis, structure, and reactivity towards [CpFe(CO)2I]

Dornhaus, Franz; Bolte, Michael; Lerner, Hans‐Wolfram

doi:10.1016/j.jorganchem.2007.03.006

Cited by 16 publications

(8 citation statements)

References 39 publications

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“…Relatedly, the protected diphosphido species [PhP(BH 3 )CH 2 CH 2 P(BH 3 )Ph] 2− was observed to act as a bridging ligand towards two [(η 5 -C 5 H 5 )-Fe(CO) 2 ] + fragments, as reported by Wagner and coworkers in 2007. 33 The addition of two equiv. of n BuLi to a THF solution of the borane derivative 3 at −78 °C resulted in formation of a new species with no P-H groups, as determined by in situ 31 P NMR spectroscopy (δ −16.2) and consistent with the desired boraneprotected dilithio compound.…”

Section: Attempted Metathesis Chemistrymentioning

confidence: 99%

Secondary diphosphine and diphosphido ligands: synthesis, characterisation and group 1 coordination compounds

et al. 2014

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Two types of secondary diphosphines, 1,8-(ArPH)2C14H8 (1a: Ar = Tripp, 2,4,6-triisopropylphenyl; 1b: Ar = Mes, 2,4,6-trimethylphenyl) and 1,3-((t)BuPHCH2)2C6H4 (2), based on rigid 1,8-anthracene and flexible m-xylyl frameworks, respectively, have been synthesized using different strategies. Compounds 1a and 1b were formed by nucleophilic aromatic substitution of a potassium organophosphido salt onto 1,8-difluoroanthracene, while compound 2 was obtained by addition of the Grignard reagent [1,3-(ClMgCH2)2C6H4]x to a dichloroorganophosphine, followed by reduction to the diphosphine. These compounds were isolated as ca. 1 : 1 mixtures of rac and meso diastereomers as determined by multinuclear NMR spectroscopy. Borane and selenide derivatives of 2, 1,3-((t)BuPH(BH3)CH2)2C6H4 (3) and 1,3-((t)BuPH(Se)CH2)2C6H4 (4), were obtained. Preferential crystallization of one diastereomer of 3 and 4 was observed; X-ray crystallographic studies identified this as the rac isomer for diselenide 4. Metallation studies of compounds 1a and 2 yielded several alkali metal salts. The reaction of KH or K metal with 1a yielded the compounds 1,8-(TrippPK)2C14H8·xTHF (5) and 1,8-(TrippPK)2C14H10·xTHF (6), respectively; in complex 6 the central aromatic ring has been reduced to yield a bent dihydroanthracene backbone. A crown ether derivative of 6, [K(18-crown-6)(THF)2]2[1,8-(TrippP)2C14H10] (7), was characterised crystallographically. Double deprotonation of compound 2 with (n)BuLi/TMEDA (TMEDA = N,N,N',N'-tetramethylethylenediamine) afforded the yellow dilithium complex 1,3-((t)BuPLiCH2)2C6H4·TMEDA (8), which crystallized as a dimer featuring lithium-arene π interactions.

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Section: Attempted Metathesis Chemistrymentioning

confidence: 99%

Secondary diphosphine and diphosphido ligands: synthesis, characterisation and group 1 coordination compounds

et al. 2014

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“…Very recently we have reported the syntheses of the diphospine PhHP-CH 2 -CH 2 -PHPh (Ph = C 6 H 5 ) (Dornhaus et al, 2007). Oxidation of the diphosphine rac/meso PhHPH-CH 2 -CH 2 -PHPh with air provides facile access to the corresponding phosphine oxide rac/meso PhHPO-CH 2 -CH 2 -OPHPh.…”

Section: S1 Commentmentioning

confidence: 99%

1,2-Bis(phenylphosphoryl)ethane

2007

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The geometric parameters of the molecule of the title compound, C14H16O2P2, are in the usual ranges. It is a meso compound with the two chiral P atoms having opposite configurations. The P—CH2—CH2—P chain adopts a trans conformation [torsion angle −178.59 (17)°]. The P=O bonds are almost coplanar with the adjacent phenyl ring [torsion angles = 3.8 (3) and 0.3 (3)°]. Whereas one of them is synclinal [torsion angle = −59.0 (2)°] to the central C—C bond, the other is anticlinal [torsion angle = 56.6 (2)°] to the central C—C bond. The dihedral angle between the two phenyl rings is 5.2 (3)°. The molecules are linked by weak C—H⋯O hydrogen bonds. They crystallize in rows running along the c axis.

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“…Wagner and coworkers also reported the solid-state structure of a related alkyl-tethered bis-(phosphido-borane) complex. 8 A small number of transition metal complexes of alkyl-tethered α,ω-diphosphides have also been reported, 9−13 along with a selection of variously substituted aryl-or alkenyl-bridged diphosphide compounds. 14−24 Our interest in alkyl-tethered α,ω-diphosphides stems from their potential use as precursors to novel cyclic diphosphatetrylenes (P-heterocyclic tetrylenes), heavier element analogues of the now ubiquitous N-heterocyclic carbenes.…”

Section: ■ Introductionmentioning

confidence: 99%

Influence of Chain Length on the Structures and Dynamic Behavior of Alkyl-Tethered α,ω-Diphosphide Complexes of Lithium and Their Use in the Synthesis ofP-Heterocyclic Stannylenes

et al. 2018

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The alkyl-tethered α,ω-diphosphines (Dipp)PH(CH2) n PH(Dipp) (n = 1 (3H), 2 (4H), 3 (5H), 4 (6H), and 5 (7H)) were prepared in good yield and characterized by multinuclear NMR spectroscopy [Dipp = 2,6-iPr2C6H3]. Treatment of 3H with 2 equiv of nBuLi and 2 equiv of TMEDA gives the diphosphide complex [CH2{P(Dipp)}2]Li2(TMEDA)2 (3Lia), which crystallizes as discrete monomers which do not exhibit temperature-dependent NMR behavior. Treatment of 4H–7H with 2 equiv of nBuLi in THF gives the diphosphides [[CH2{P(Dipp)}]2]2Li4(THF)2(OEt2)2 (4Li), [CH2{CH2P(Dipp)}2]Li2(THF)4 (5Li), [{CH2CH2P(Dipp)}2]Li2(THF)6 (6Li), and [CH2{CH2CH2P(Dipp)}2]2Li4(THF)6·PhMe (7Li) after crystallization. Compounds 4Li–7Li adopt either monomeric or dimeric structures in the solid state, depending on the length of the alkyl tether of the diphosphide ligand. In solution, compounds 4Li–7Li exhibit dynamic behavior: variable-temperature 31P{1H} and 7Li NMR spectroscopic studies indicate that this involves equilibria between monomeric and dimeric or higher oligomeric species with the nature of the equilibrium again depending on the length of the alkyl tether of the diphosphide ligand. The reactions between 3Li, 6Li, or 7Li and SnCl2 in THF give mixtures of products which could not be separated. In contrast, the reactions between 4Li or 5Li and 1 equiv of SnCl2 give the dimeric P-heterocyclic stannylenes [{CH2P(Dipp)}2Sn]2 (4Sn) and [CH2{CH2P(Dipp)}2Sn]2.1/2THF (5Sn), respectively. While compound 5Sn is isolated exclusively as the cis isomer, 4Sn is isolated as a mixture of cis and trans isomers in an approximate 5:1 ratio. The solid-state structures of trans-4Sn and cis-5Sn were obtained, and multinuclear NMR spectroscopy indicates that the dimeric structures of these compounds are maintained in solution. Compounds 4Sn and 5Sn represent the first P-heterocyclic stannylene dimers to be structurally characterized.

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The first bidentate phosphanylborohydride: Synthesis, structure, and reactivity towards [CpFe(CO)2I]

Cited by 16 publications

References 39 publications

Secondary diphosphine and diphosphido ligands: synthesis, characterisation and group 1 coordination compounds

Secondary diphosphine and diphosphido ligands: synthesis, characterisation and group 1 coordination compounds

1,2-Bis(phenylphosphoryl)ethane

Influence of Chain Length on the Structures and Dynamic Behavior of Alkyl-Tethered α,ω-Diphosphide Complexes of Lithium and Their Use in the Synthesis ofP-Heterocyclic Stannylenes

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