Template Synthesis of the First 1,4,7-Triphosphacyclononane Derivatives

Edwards, P; Newman, Paul D.; Malik, K. M. Abdul

doi:10.1002/1521-3773(20000818)39:16<2922::aid-anie2922>3.0.co;2-s

Cited by 41 publications

(66 citation statements)

References 11 publications

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“…The CH 3 CN ligand in 4 is readily exchanged by phenylphosphine to give the diphosphine-monophosphine complex [(η 4 -C 4 Me 4 )Co(dfppb)(PH 2 Ph)] + (5). No obvious color The molecular structures of 4 and 5 determined by singlecrystal X-ray crystallography are shown in Figure 2.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Peripheral Methyl Activation in η⁴-1,2,3,4-Tetramethylcyclobutadienylcobalt Complexes: Template Synthesis and Subsequent Reactivity of Triphosphamacrocycles

et al. 2014

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The cationic complex (η 4 -1,2,3,4-tetramethylcyclobutadienyl)cobalt(trisacetonitrile), [(η 4 -C 4 Me 4 )Co-(NCCH 3 ) 3 ] + (1), allows the stepwise introduction of suitable phosphine precursors to the [(η 4 -C 4 Me 4 )Co] + fragment by replacement of the labile acetonitrile ligands. These reactions give rise to the piano-stool complexes [(η 4 -C 4 Me 4 )Co(dppe)-(NCCH 3 )] + (2), [(η 4 -C 4 Me 4 )Co(dppe)(PH 2 Ph)] + (3), [(η 4 -C 4 Me 4 )Co(dfppb)(NCCH 3 )] + (4), and [(η 4 -C 4 Me 4 )Co(dfppb)-(PH 2 Ph)] + (5), where dfppb = 1,2-bis{di(2-fluorophenyl)phosphino}benzene and dppe = 1,2-bis(diphenylphosphino)ethane. Complex 5 is a template for the synthesis of the P 3 macrocycle complex [(η 4 -C 4 Me 4 )Co{1,4-bis(2-fluorophenyl)-7-phenyl[b,e,h]tribenzo-1,4,7-triphosphacyclononane}] + (6), through base-promoted intramolecular macrocyclization. The hydrogens of two of the ring methyls of the tetramethylcyclobutadienyl ligand in the macrocycle complex 6 are sufficiently acidic to undergo deprotonation by KO t Bu, promoting nucleophilic attack at the fluorine-bearing ortho-carbons of the 2-fluoroaryl groups on two of the phosphorus donors in 6. The resultant hemi-incarcerand complex [{η 4 ,κP,κP,κP-Me 2 C 4 -[1,4-bis(2-CH 2 C 6 H 4 )-7-C 6 H 5 -[b,e,h]tribenzo-1,4,7-triphosphacyclononane]-1,2}Co] + (cis-7) contains a hybrid phosphorus/carbon donor ligand where the P 3 macrocycle is connected to the cyclobutadienyl function through two cis-2-methylphenyl links. The new complexes have been characterized fully by spectroscopic and analytical techniques including single-crystal X-ray structure determinations of 2, 3, 4, 5, 6, and cis-7. ■ INTRODUCTIONIn contrast to triaza and trithia macrocycles with variable ring sizes, related P-donor triphospha macrocycle ligands, which may have the ability to stabilize low and unusual metal oxidation states, remain rare. The common method of combining suitably functionalized precursors in dilute solution to yield the desired macrocycle cannot be applied easily to the synthesis of phosphorus macrocycles because of experimental difficulties associated with handling the often volatile, noxious, toxic, and air-sensitive phosphine precursors and intermediates. Aside from the necessary need for large volumes of solvent, a further drawback of the direct method is a lack of stereochemical control, which results in an isomeric mixture of phosphamacrocycles due to the relatively high inversion energy barrier at P; this has recently been confirmed in the highdilution solution synthesis of 1,4,7-triphenyl-1,4,7-triphosphacyclononane (9-aneP 3 Ph 3 ). 1 Template methods provide a means of controlling the stereochemistry but are often hampered by difficulties associated with the release of the macrocycle. Details of successful direct and template approaches to macrocyclic phosphines and aspects of their coordination chemistry appear in a recent review by Swor and Tyler. 2 Much of our interest in triphosphorus macrocycles stems from their expected ability to form thermodynamically and kinetical...

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Section: ■ Results and Discussionmentioning

confidence: 99%

Peripheral Methyl Activation in η⁴-1,2,3,4-Tetramethylcyclobutadienylcobalt Complexes: Template Synthesis and Subsequent Reactivity of Triphosphamacrocycles

et al. 2014

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“…This might result from the flexibility of the 12-membered macrocycle as well as stereochemically nonrigid (and intrinsically more reactive) seven-coordination. Consequently, smaller ring macrocycles might be expected to form more stable systems and the study of 9-, [26,27] 10-, [28] and 11-membered triphosphorus macrocycles is in progress.…”

Section: Resultsmentioning

confidence: 99%

“…All other chemicals were dried over molecular sieves (liquids) or used as received (Aldrich). The compounds TiCl 4 (THF) 2 , ZrCl 4 (THF) 2 , HfCl 4 (THF) 2 , TiCl 3 (THF) 3 , VCl 3 (THF) 3 , [29] NbCl 4 (THF) 2 , NbCl 3 (DME), [30] Nb(O)Cl 3 (MeCN) 2 , [26] [12]aneP 3 Et 3 , [4] [12]aneP 3 Et 3 Cr(CO) 3 , and ([12]aneP 3 R 3 )Cr(CO) 3 (R ϭ CH 3 OC 3 H 6 . C 2 H 5 OC 2 H 4 ) [22] were prepared by literature methods.…”

Section: Methodsmentioning

confidence: 99%

Early Transition Metal Complexes of Triphosphorus Macrocycles

Baker

Davies

Edwards

et al. 2002

Eur. J. Inorg. Chem.

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The reactions of 1,5,9-triethyl-1,5,9-triphosphacyclododecane, [12]aneP 3 Et 3 , with first-row transition metal halides MCl 3 [M = Ti (1), V (2), and Cr (3)] or their THF adducts are reported. The oxidation of 2 gives the complex ([12]aneP 3 Et 3 )-V(O)Cl 2 (4). This is the first example of a phosphane ligand that is trans to a vanadyl moiety. Also reported are V III (5) and Cr III (6) complexes of the pendant ether macrocycles [12]aneP 3 (C 2 H 4 OEt) 3 and 12[ane]P 3 (C 3 H 6 OMe) 3 respectively. The complexes 1−6 have been characterised crystallographically and represent a rare class of phosphane com-

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“…No metal complexes of the ligand were reported but the methyl iodide salt [9] The majority of the reports related to [9]aneP 3 type cyclononane ligands has arisen from one group, much of the chemistry utilising the activated, electrophilic ortho-fluorophenyl substituent on a neighbouring pnictide donor [288][289][290][291][292][293][294][295][296][297][298][299].…”

Section: Synthesismentioning

confidence: 99%

Cyclononanes: The extensive chemistry of fundamentally simple ligands

Gahan

2016

Coordination Chemistry Reviews

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The cyclononane ligands are fundamental examples of the macrocyclic ligand. With three donor atoms in a nine-membered ring they represent the simplest of the macrocyclic class. However, this simplicity is deceptive, for within this class the variations are extensive and perhaps hitherto unrecognized. As well as the relatively familiar 1,4,7-triaza-([9]aneN 3) and 1,4,7-trithia-([9]aneS 3) cyclononanes whole families of cyclononane ligands are known with thioether/nitrogen, nitrogen/oxygen, selenium, tellurium as well as phosphorus and arsenic donors. The chemistry of some of these ligands, for example [9]aneN 2 S, [9]aneNS 2 and [9]aneN 2 O has been reported extensively, and some examples have simply been reported as having been synthesised (for example [9]aneO 2 S and [9]aneO 2 Se) with little other information. This review attempts to introduce the extensive chemistry of what are fundamentally the simplest examples of macrocyclic ligands. 1. Highlights Review of current trends in cyclononane chemistry Diversity of donor groups and transition metal chemistry complexes which arise Significant new synthetic chemistry Significant advances in the applications of cyclononane ligands

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Template Synthesis of the First 1,4,7-Triphosphacyclononane Derivatives

Cited by 41 publications

References 11 publications

Peripheral Methyl Activation in η⁴-1,2,3,4-Tetramethylcyclobutadienylcobalt Complexes: Template Synthesis and Subsequent Reactivity of Triphosphamacrocycles

Peripheral Methyl Activation in η⁴-1,2,3,4-Tetramethylcyclobutadienylcobalt Complexes: Template Synthesis and Subsequent Reactivity of Triphosphamacrocycles

Early Transition Metal Complexes of Triphosphorus Macrocycles

Cyclononanes: The extensive chemistry of fundamentally simple ligands

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Template Synthesis of the First 1,4,7-Triphosphacyclononane Derivatives

Cited by 41 publications

References 11 publications

Peripheral Methyl Activation in η4-1,2,3,4-Tetramethylcyclobutadienylcobalt Complexes: Template Synthesis and Subsequent Reactivity of Triphosphamacrocycles

Peripheral Methyl Activation in η4-1,2,3,4-Tetramethylcyclobutadienylcobalt Complexes: Template Synthesis and Subsequent Reactivity of Triphosphamacrocycles

Early Transition Metal Complexes of Triphosphorus Macrocycles

Cyclononanes: The extensive chemistry of fundamentally simple ligands

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Product

Resources

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Peripheral Methyl Activation in η⁴-1,2,3,4-Tetramethylcyclobutadienylcobalt Complexes: Template Synthesis and Subsequent Reactivity of Triphosphamacrocycles

Peripheral Methyl Activation in η⁴-1,2,3,4-Tetramethylcyclobutadienylcobalt Complexes: Template Synthesis and Subsequent Reactivity of Triphosphamacrocycles