Monoanionic N,P,S‐Janus Head Tripods in s‐Block Metal Coordination

Meinholz, Margret M.

doi:10.1002/ejic.201100658

Cited by 18 publications

(15 citation statements)

References 73 publications

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“…The explanation for that might be the diagonal relationship between lithium and magnesium in the periodic tables of elements and their similar cationic radius. For any other successful transmetalation reactions of S ‐phosphanyl‐diimidosulfinate ligands reported in this paper, metal(II) bis(trimethylsilyl)amides were used 12b. Despite of those limitations, we now reacted 1 with metal(II) bromides to investigate whether or not the S VI ligand is stable enough against redox scrambling.…”

Section: Resultsmentioning

confidence: 99%

Polyimido Sulfur(VI) Phosphanyl Ligand in Metal Complexation

Carl¹

2014

Chemistry A European J

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Herein, new complexes containing the [Ph2PCH2S(NtBu)3](-) anion are presented, supplying three imido nitrogen atoms and a remote phosphorus atom as potential donor sites to main group and transition-metal cations. The lithiated complex [(tmeda)Li{(NtBu)3SCH2PPh2}] (1) is an excellent starting material in transmetalation reactions. Herein, the transition-metal complexes [M{(NtBu)3SCH2PPh2}2] (M=Mn (2), Ni (3), Zn (4)) were synthesized and structurally characterized. Their isotypical molecules show SN2 chelation and no employment of the adjacent phosphorus atom in coordination. The third pendent imido group is always twisted toward the vacant face of the tetrahedrally coordinated sulfur atom.

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Section: Resultsmentioning

confidence: 99%

Polyimido Sulfur(VI) Phosphanyl Ligand in Metal Complexation

Carl¹

2014

Chemistry A European J

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“…Due to this fact the phosphane bases are commonly incorporated into the anions leading to multidentate anions. Nevertheless, a variety of phosphane complexes of magnesium (see e.g., [12][13][14][15][16]) and calcium (see e.g., [15][16][17][18][19]) have been isolated and structurally studied. In order to stabilize magnesium-and calcium-based Grignard reagents, phosphanylmethyl substituents in ortho-position of the arylalkaline earth metal halides seem to be a suitable choice.…”

Section: Introductionmentioning

confidence: 99%

Reduction of Bromo- and Iodo-2,6-bis(diphenylphosphanylmethyl)benzene with Magnesium and Calcium

et al. 2016

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Arylmagnesium and -calcium reagents are easily accessible; however, ether degradation processes limit storability, especially of the calcium-based heavy Grignard reagents. Ortho-bound substituents with phosphanyl donor sites usually block available coordination sites and stabilize such complexes. The reaction of bromo-2,6-bis(diphenylphosphanylmethyl)benzene (1a) with magnesium in tetrahydrofuran yields [Mg{C 6 H 3 -2,6-(CH 2 PPh 2 ) 2 } 2 ] (2) after recrystallization from 1,2-dimethoxyethane. However, the similarly performed reduction of bromo-(1a) and iodo-2,6-bis(diphenylphosphanylmethyl)benzene (1b) with calcium leads to ether cleavage and subsequent degradation products. α-Deprotonation of tetrahydrofuran (THF) yields 1,3-bis(diphenylphosphanylmethyl)benzene. Furthermore, the insoluble THF adducts of dimeric calcium diphenylphosphinate halides, [(thf) 3 Ca(X)(µ-O 2 PPh 2 )] 2 [X = Br (3a), I (3b)], precipitate verifying ether decomposition and cleavage of P-C bonds. Ether adducts of calcium halides (such as [(dme) 2 (thf)CaBr 2 ] (4)) form, supporting the initial Grignard reaction and a subsequent Schlenk-type dismutation reaction.

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“…[12][13][14][15][16]) and calcium [see e.g. [15][16][17][18][19] have been isolated and structurally studied.…”

Section: Introductionmentioning

confidence: 99%

Reduction of Bromo- and Iodo-2,6-bis(diphenylphosphanylmethyl)benzene with Magnesium and Calcium

Koch

Krieck

Görls

et al. 2016

Preprint

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Arylmagnesium and -calcium reagents are easily accessible, however, ether degradation processes limit the storability especially of the calcium-based heavy Grignard reagents. Ortho-bound substituents with phosphanyl donor sites usually block available coordination sites and stabilize such complexes. The reaction of bromo-2,6-bis(diphenylphosphanylmethyl)benzene (1a) with magnesium in tetrahydrofuran yields [Mg{C6H3-2,6-(CH2PPh2)2}2] (2) after recrystallization from 1,2-dimethoxyethane. However, the similarly performed reduction of bromo- (1a) and iodo-2,6-bis(diphenylphosphanylmethyl)benzene (1b) with calcium leads to ether cleavage and subsequent degradation products. α-Deprotonation of THF yields 1,3-bis(diphenylphosphanylmethyl)benzene. Furthermore, the insoluble THF adducts of dimeric calcium diphenylphosphinate halides, [(thf)3Ca(X)(µ-O2PPh2)]2 [X = Br (3a), I (3b)], precipitate verifying ether decomposition and cleavage of P-C bonds. Ether adducts of calcium halides [such as [(dme)2(thf)CaBr2] (4)] form supporting the initial Grignard reaction and a subsequent Schlenk-type dismutation reaction.

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Monoanionic N,P,S‐Janus Head Tripods in s‐Block Metal Coordination

Cited by 18 publications

References 73 publications

Polyimido Sulfur(VI) Phosphanyl Ligand in Metal Complexation

Polyimido Sulfur(VI) Phosphanyl Ligand in Metal Complexation

Reduction of Bromo- and Iodo-2,6-bis(diphenylphosphanylmethyl)benzene with Magnesium and Calcium

Reduction of Bromo- and Iodo-2,6-bis(diphenylphosphanylmethyl)benzene with Magnesium and Calcium

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