P6 Manganocene and P3 Cymantrene: Consequences of the Inclusion of Phosphorus Atoms in Mn-Coordinated Cyclopentadienyl Ligands

Clark, Timothy; Elvers, Achim; Heinemann, Frank W.; Hennemann, Matthias; Zeller, Mat­thias; Zenneck, Ulrich

doi:10.1002/1521-3773(20000616)39:12<2087::aid-anie2087>3.0.co;2-b

Cited by 34 publications

(28 citation statements)

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“…The molecular structure (Figure 2, Tables 1 and 3) confirms the estimated bonding mode with the triphospholyl moiety again being η 5 the angle built up by the two co-ligands being 90.7°. In contrast with 4, the orientation of the co-ligands is now in parallel with the vertical mirror plane of the π-ligand and the bulky triphenylphosphane is situated in a trans position with respect to the single phosphorus atom P3.…”

Section: Resultssupporting

confidence: 55%

“…Due to its phosphorus lone pairs 3 reacts with (thf)-(CO) 5 Cr to yield the binuclear manganese chromium complex {µ[1:1-5-η-t-Bu 2 C 2 P 3 ]}{(CO) 5 Cr}{(CO) 3 Mn}. 5 Therefore photolysis of (η 5 -t-Bu 2 C 2 P 3 )(CO) 3 Mn (3) without addition of further ligands was attempted. Within Co-C(10) 1.725(4) Co-P (4) 2.1760(10) P(1)-P(2) 2.1620(14) 15 min 1 equiv of carbon monoxide is removed and replaced by a phosphorus atom of a second triphospholyl complex to result in the formation of homobinuclear species.…”

Section: Resultsmentioning

confidence: 99%

“…(η 5 -t-Bu2C2P3)(CO){P(CH2CH3)3}Co (5). At 0°C 79 mg (0.228 mmol) of (η 5 -t-Bu2C2P3)(CO)2Co (4) and 0.5 mL of triethylphosphane (0.4 g, 3.4 mmol) in 80 mL of n-hexane are irradiated in a Pyrex glass apparatus for 10 min with a 125 W high-pressure mercury lamp.…”

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Ligand Exchange Reactions of Triphospholyl Metal Carbonyl Complexes

et al. 2001

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Utilizing 1-triphenylstannyl-3,5-di(tert-butyl)-1,2,4-triphosphole (2) as the transfer reagent for the 1,2,4-triphospholyl ligand, the new cobalt dicarbonyl complex (η 5 -t-Bu 2 C 2 P 3 )(CO) 2 Co (4) has been prepared. The reactivity of 4 and that of triphosphacymantrene (η 5 -tBu 2 C 2 P 3 )(CO) 3 Mn (3) toward carbonyl exchange have been investigated. When 3 or 4 are photolyzed in the presence of phosphanes the mono-and disubstituted complexes (η 5 -t- (5), Ph (6)) and (η 5 -t-Bu 2 C 2 P 3 )(CO)(PMe 3 ) 2 Mn (7) are obtained. In the absence of additional ligands, the irradiation of 3 in n-hexane results in the formation of the dinuclear rac and meso complexes {µ[1:1-5-η-t-Bu 2 C 2 P 3 ](CO) 2 Mn} 2 (8a and 8b). Under thermal conditions the carbonyl ligands of both 3 and 4 are replaced by isonitrile ligands to yield (η 5 -t-Bu 2 C 2 P 3 )(CN-Cy) 2 Co (9), (η 5 -t-Bu 2 C 2 P 3 )(CO)(CN-Cy)Co (10), and (η 5 -t-Bu 2 C 2 P 3 )-(CO) 2 (CN-Cy)Mn (11), respectively. The substances have been fully characterized including X-ray structural analysis for the complexes 4, 6, 7, 8a, 8b, and 9. Under both photochemical and thermal conditions the complexes 3 and 4 are much more reactive than their phosphorusfree cyclopentadienyl analogues. In contrast with cymantrene, triphosphacymantrene (3) seems to react via an associative pathway.

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Section: Resultssupporting

confidence: 55%

Section: Resultsmentioning

confidence: 99%

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Ligand Exchange Reactions of Triphospholyl Metal Carbonyl Complexes

et al. 2001

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“…phosphaferrocenes, phosphacymantrenes, phosphazirconocenes, etc. [4][5][6] The 1,2,4triphosphacyclopentadienide (Cp 1,2,4-P3 ) and 1,3-diphosphacyclopentadienide (Cp 1,3-P 2 ) ligands realize η 5 coordination in tri/penta/hexaphosphaferrocene [7][8][9] or triphosphacymantrene 10,11 derivatives, mixed η 5 /η 4 in [Co(η 5 -Cp 1,2,4-P3 )(η 4 -Cp 1,2,4-P3 )], 12 η 5 /η 3 in [Ni(η 5 -Cp 1,3-P 2 )(η 3 -Cp 1,3-P 2 )], 13 η 3 in [Mo(η 5 -Cp)(η 3 -Cp 1,2,4-P 3 )], 14 and bridging (μ:η 1 ,η 1 ) in Cu I (ref. 15) and Ni II (ref.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and magnetic properties of manganese carbonyl complexes with different coordination modes of 3,4,5-triaryl-1,2-diphospholide ligands

et al. 2015

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The set of complexes bis-(μ:η(1),η(1)-3,4,5-triaryl-1,2-diphosphacyclopentadienyl)-bis-(tetracarbonyl manganese(i)) (aryl = C6H5 (), p-FC6H4 (), p-ClC6H4 ()) undergo an irreversible rearrangement to mononuclear 3,4,5-triaryl-1,2-diphosphacymantrenes (). According to quantum-chemical calculations binuclear complexes can be considered to be products of kinetic control and mononuclear species are thermodynamically favorable compounds. The antiferromagnetic intramolecular interaction observed for complexes can be effectively tuned by using substituents in the para-position of the arene ring, whereas mononuclear 1,2-diphosphacymantrenes are diamagnetic.

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“…An additional benefit is that the silyl group may readily be adapted to allow fixation of the catalyst on solid supports [3][4][5]. An alternative approach, which imparts similar electron withdrawing properties on cyclopentadienyl units, is the substitution of CH vertices in the ring for isolobal P centres, a strategy that is known to promote d-backbonding from the metal to the ring [6][7][8]. However, the combination of these concepts, i.e.…”

Section: Introductionmentioning

confidence: 99%