The Diphosphorus Complex [Cp2Mo2(CO)4(η2‐P2)] as a Building Block for the Synthesis of Mixed‐Hybrid Coordination Polymers

Moussa, Mehdi Elsayed; Attenberger, Bianca; Fleischmann, M.; Schreiner, Andrea; Scheer, Manfred

doi:10.1002/ejic.201600895

Cited by 18 publications

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“…The P 2 unit is oriented perpendicularly with respect to the intermetallic vector,r esultingi natetrahedral m,h 2 geometry.T he P1ÀP2 distance of 2.089(3) is similartothat in known diphosphorus-bridged complexes. [17] The C1ÀC2 distance of the bent alkynel igand is 1.34 (1) ,t he tert-butyl substituents enclose CÀCÀCa ngles of 141.1(8)8 and 144.8(8)8,r espectively.S imilar structuralp arameters are found in other alkyne-bridged diruthenium complexes. [18] The Ru1ÀRu2 distance of 2.6985(8) is 0.2 larger than the sum of covalent radii.…”

Section: Resultsmentioning

confidence: 99%

“…[17] The C1ÀC2 distance of the bent alkynel igand is 1.34(1) ,t he tert-butyl substituents enclose CÀCÀCa ngles of 141.1(8)8 and 144.8(8)8,r espectively.S imilar structuralp arameters are found in other alkyne-bridged diruthenium complexes. The structure consists of ad iphosphorusm oiety and an alkyne (2,2,5,5-tetramethylhex-3-yne) bridging a Cp*RuRuCp* unit.…”

Section: ]Bfmentioning

confidence: 99%

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Flexidentate Coordination Behavior and Chemical Non‐Innocence of a Bis(1,3‐Diphosphacyclobutadiene) Sandwich Anion

Rödl

Wolf

2019

Chemistry A European J

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The homoleptic 1,3-diphosphacyclobutadiene sandwich complex [Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 ] À behaved as av ersatile and highly flexible metalloligand toward Ni 2 + ,R u 2 + , Rh + ,a nd Pd 2 + cations, formingarange of unusual oligonuclear compounds. The reactiono f[ K(thf) 2 {Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 }] with [Ni 2 Cp 3 ]BF 4 initially afforded the s-complex [CpNi{Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 }(thf)] (2), which converted into [Co(h 4 -CpNi{1,3-P 2 C 2 tBu 2 -kP,kC})(h 4 -1,3-P 2 C 2 tBu 2 )] (3)b elow room temperature. The structure of 3 contains an unprecedented 1,4-diphospha-2-nickelacyclopentadiene moiety formed by an oxidative addition of al igand PÀCb ond onto nickel. At elevated temperatures, 3 isomerized to [Co(h 4 -CpNi{1,4-P 2 C 2 tBu 2 -k 2 P, P })(h 4 -1,3-P 2 C 2 tBu 2 )] (4), which features a1 ,3-diphospha-2-nickelacyclopentadiene unit. Transmetalation of [K(thf) 2 {Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 }] with [Cp*RuCl] 4 (Cp* = C 5 Me 5 )a fforded tetranuclear[ (Cp*Ru) 3 (m-Cl) 2 {Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 }] (5), in which the [Co(h 4 -1,3-P 2 C 2 tBu 2 ] À aniona cts as ac helate ligand toward Ru 2 + .T he diphosphido complex [(Cp*Ru) 2 (m,h 2 -P 2 )(m,h 2 -C 2 tBu 2 )] (6)w as formed as ab yproduct. Pure compound 6 was isolated after prolonged heating of the reaction mixture. The reaction of [K(thf) 2 {Co(h 4 -1,3-P 2 C 2 R 2 ) 2 }] (R = tBu;a damantyl, Ad) with [RhCl(cod)] 2 (cod = 1,5-cyclooctadiene) afforded unprecedented p-complexes [Rh(cod){Co(h 4 -1,3-P 2 C 2 R 2 ) 2 }] (7:R = tBu; 8:R= Ad), in which one m:h 4 :h 4 -P 2 C 2 R 2 ligand bridges two metal atoms.T he pentanuclear complex [Pd 3 (PPh 3 ) 2 {Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 } 2 ]( 10), featuring aP d 3 chain andarare 1,4-diphospha-2-butene ligand,w as synthesized by reacting [K(thf) 2 {Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 }] with cis-PdCl 2 (PPh 3 ) 2 .T he redox properties of selected compounds were analyzed by cyclic voltammetry, whereas DFT calculations gave additional insighti ntot he electronic structures.The results of this study revealed several remarkable and previously unrecognized properties of the [Co(P 2 C 2 tBu 2 ) 2 ] À anion.Scheme1.Synthesis of complexes of type A. [7] [a] C. Rçdl,P rof. Dr.R.W olf

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confidence: 99%

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confidence: 99%

Flexidentate Coordination Behavior and Chemical Non‐Innocence of a Bis(1,3‐Diphosphacyclobutadiene) Sandwich Anion

Rödl

Wolf

2019

Chemistry A European J

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Der cyclo‐P₄‐Sandwichkomplex des Cobalts und seine Rolle bei der Bildung von Polyphosphorverbindungen

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The Cobalt cyclo‐P₄ Sandwich Complex and Its Role in the Formation of Polyphosphorus Compounds

et al. 2017

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A synthetic approach to the sandwich complex [Cp′′′Co(η4‐P4)] (2) containing a cyclo‐P4 ligand as an end‐deck was developed. Complex 2 is the missing homologue in the series of first‐row cyclo‐Pn sandwich complexes, and shows a unique tendency to dimerize in solution to form two isomeric P8 complexes [(Cp′′′Co)2(μ,η4:η2:η1‐P8)] (3 and 4). Reactivity studies indicate that 2 and 3 react with further [Cp′′′Co] fragments to give [(Cp′′′Co)2(μ,η2:η2‐P2)2] (5) and [(Cp′′′Co)3P8] (6), respectively. Furthermore, complexes 2, 3, and 4 thermally decompose forming 5, 6, and the P12 complex [(Cp′′′Co)3P12] (7). DFT calculations on the P4 activation process suggest a η3‐P4 Co complex as the key intermediate in the synthesis of 2 as well as in the formation of larger polyphosphorus complexes via a unique oligomerization pathway.

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The Diphosphorus Complex [Cp₂Mo₂(CO)₄(η²‐P₂)] as a Building Block for the Synthesis of Mixed‐Hybrid Coordination Polymers

Cited by 18 publications

References 69 publications

Flexidentate Coordination Behavior and Chemical Non‐Innocence of a Bis(1,3‐Diphosphacyclobutadiene) Sandwich Anion

Flexidentate Coordination Behavior and Chemical Non‐Innocence of a Bis(1,3‐Diphosphacyclobutadiene) Sandwich Anion

Der cyclo‐P₄‐Sandwichkomplex des Cobalts und seine Rolle bei der Bildung von Polyphosphorverbindungen

The Cobalt cyclo‐P₄ Sandwich Complex and Its Role in the Formation of Polyphosphorus Compounds

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The Diphosphorus Complex [Cp2Mo2(CO)4(η2‐P2)] as a Building Block for the Synthesis of Mixed‐Hybrid Coordination Polymers

Cited by 18 publications

References 69 publications

Flexidentate Coordination Behavior and Chemical Non‐Innocence of a Bis(1,3‐Diphosphacyclobutadiene) Sandwich Anion

Flexidentate Coordination Behavior and Chemical Non‐Innocence of a Bis(1,3‐Diphosphacyclobutadiene) Sandwich Anion

Der cyclo‐P4‐Sandwichkomplex des Cobalts und seine Rolle bei der Bildung von Polyphosphorverbindungen

The Cobalt cyclo‐P4 Sandwich Complex and Its Role in the Formation of Polyphosphorus Compounds

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The Diphosphorus Complex [Cp₂Mo₂(CO)₄(η²‐P₂)] as a Building Block for the Synthesis of Mixed‐Hybrid Coordination Polymers

Der cyclo‐P₄‐Sandwichkomplex des Cobalts und seine Rolle bei der Bildung von Polyphosphorverbindungen

The Cobalt cyclo‐P₄ Sandwich Complex and Its Role in the Formation of Polyphosphorus Compounds