Darstellung, Eigenschaften sowie Reaktionen metallhaltiger Heterocyclen. LXVI. Nickelinduzierte Cyclocodimerisierung eines Thioxophosphor(V)‐Kations mit einem aktivierten Alkin

Lindner, Ekkehard; Nothdurft, A.

doi:10.1002/zaac.19895790123

Zeitschrift anorg allge chemie

1989

DOI: 10.1002/zaac.19895790123

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Darstellung, Eigenschaften sowie Reaktionen metallhaltiger Heterocyclen. LXVI. Nickelinduzierte Cyclocodimerisierung eines Thioxophosphor(V)‐Kations mit einem aktivierten Alkin

Ekkehard Lindner

A. Nothdurft

Abstract: Durch Einwirkung von Di‐tert‐butylthioxophosphoran (t‐Bu)2P(H)S auf Nickelocen in Ether erhält man den ersten kinetisch stabilisierten (η2‐Diorganothioxophosphor)‐ nickel‐Komplex [(η5‐C5H5)Ni(η2‐SP(t‐Bu)2)] (1). Bei Anwesenheit des Acetylendicarbonsäure‐dimethylesters H3CO2CCCCO2CH3 tritt mit (t‐Bu),PS Cyclocodimerisierung ein, unter Bildung des S‐ bzw. P‐isomeren Thiaphosphanickelacyclopentadiens (η5‐C5H5) (2S) und Thiaphosphanickelacyclopentens (η5‐C5H5)(2P) (RCO2CH3). Die Zusammensetzung und Struktur de… Show more

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Cited by 9 publications

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“…The ligand precursor used for cross-coupling reactions was straightforwardly synthesized by reaction of ( t -Bu) 2 PH with S 8 in benzene and characterized by X-ray crystallography (see the Supporting Information for full details), and an ORTEP view is shown in Figure 1 ORTEP view (50% probability) of di- tert -butylphosphine sulfide.…”

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Air-Stable Phosphine Sulfide Ligand Precursors for Nickel-Catalyzed Cross-Coupling Reactions of Unactivated Aryl Chlorides with Aryl Grignard Reagents

Marshall

2002

Organometallics

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Air-Stable Phosphine Sulfide Ligand Precursors for Nickel-Catalyzed Cross-Coupling Reactions of Unactivated Aryl Chlorides with Aryl Grignard Reagents

Marshall

2002

Organometallics

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Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LXXVII Synthese, Struktur und Reaktivität von Phosphametallacyclopropanen mit isolobalen ER‐ (E = N, P, As, Sb) und Fe(CO)₄‐Bausteinen

et al. 1991

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The phosphidometallates Liz{ [M]"PPh,) {[MI = (q5-C5H5)M-(CO),), resulting from the metal hydride complexes H[M]PPh,H [M = Cr (11, Mo (21, W (3)] by reduction with nBuLi, react with the geminal dihalides REClz to give the three-membered phosphametallacyclopropanes [ M -R [ER = NC6F5 (M = Cr (la), Mo (2a), W (3a)), PPh (M=Cr (lb), Mo (2b), W (3b)), PC6HII (M=Cr (lc), Mo (2c), W (3c)), P-tBu (M=Cr (ld), Mo (2d), W (3d)), P(2,4,6-(tB~)~C&~) (M=Cr (le), Mo (Ze), W (3e)), As(2,4,6-(tB~)~C~H~) (M= Cr ( l f ) , Mo (2f), W (3f)), Sb-tBu (M=Cr (lg), Mo (2g))l. Reaction of Br,Fe(CO), with the corresponding dilithium compounds Li,([M]=PPh,] affords the phosphido-bridged heterodimetallic complexes [ M m e -(CO), [M= Cr (lh), Mo (2h), W (3h)j. According to X-ray structural analyses in 2a and 2f the P -E bond distances are shortened while the Mo -E bonds are significantly elongated compared to a single bond. (OC)5CrTHF is added to the Lewis basic E atom in 2b, 2d, and 2g with loss of THF to give [ M m R C r ( C O ) 5 [ER=PPh (4b), P-tBu (4d), Sb-tBu (4g)l.By this reaction the antimony-containing ring 2g is kinetically stabilized. Because of the low basicity of the N atom in 2a no addition was observed. The ring skeleton of 4b and 4g, undergoes no change by Cr(CO)5 coordination as shown by Xray structural analyses.

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Preparation, Properties, and Reactions of Metal‐Containing Heterocycles, XCI. Insertion of Activated Alkynes and Sulfur into the P‐P Bond of Diphosphamolybdacyclopropanes

et al. 1995

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The insertion of the alkynes ZC=CZ (2a-i) [Z = C02R: R = Me (a), Et (b), nPr (c), iPr (a), nBu ( e ) , tBu (f), neo-Pent ( g ) , cyc-Hex (h); Z = CF, (i)] into the P1-P2 bond of the diphosphamolybdacyclopropane (if-C5H5)(OC)2hiio-P1Ph2-fi2Mes (1) (Mes = 2,4,6-trimethylphenyl) results in the formation of the diphosphamolybdacyclopentenes ( T~~-C~H~) ( O C )~-hiio-P1Ph2-CZ=CZ-P2Mes (3a-i). According to an X-ray structural analysis, 3a crystallizes in the space group P2,lc with the mesityl function at P2 and the cyclopentadienyl fragment at the metal atom on the opposite side of the planar five-membered ring. The same orientation is found in solution by NMR experiments (NOE; 2D 'H, 13C HETCOR). Kinetic investigations confirm that the rate constants decrease in the sequence R = Me > Et > nPr > isoProp > Cy > nBu > neo-Pent > tBu. The second-order reaction and the strongly negative activation entropy which was determined in the case of the reaction 1 + 2e -+ 3e are consistent with a nucleophilic attack of P2 at one of the triply bonded carbon atoms of the alkyne. The reaction of 3a, h with sulfur affords the diastereomeric compounds (q5-C5Hs)(OC)2kfo-P1-Ph2-CZ=CZ-PZ(S)Mes (4a, h). An X-ray structural analysis of the heterocycle 4h, which crystallizes in the space group P i , shows the presence of the enantiomeric pair SWRS. C5H5)(OC)2bho-P1Ph2-S-P2(S)Mes-$ (6) which crystallizesin the space group Pi. The five-membered ring in 6 has an envelope conformation. Upon thermally induced cleavage of the P2S2Mes fragment from 6 the three-membered ring (q5-C5H5)(OC)2hiio-P1Ph2-$ (?) is formed as the final product.The transition metal-catalyzed or -mediated cyclooligomerization of alkynes with heteroalkynes offers a well developed method for the preparation of four-and six-membered organic heterocycle~ [~~~]. Recently, it could be demonstrated that the P-S group in thiaphosphametallacyclopropanes behaves like a heteroalkyne because of similar covalent radii and comparable electronegativities of the phosphorus and sulfur atomL4]. It is therefore suitable for a metal-mediated cyclo-cotrimerization with alkynes. Starting from the threemembered heterocycles [ M W , we obtained regiospecifically substituted thiophenesL5I, phosphole and furansL7I, respectively, which are obtained by oxidative or hydrolytic degradation of the resulting metallabicycloheptadienes. The latter were formed via the intermediately occurring thiaphosphametallacyclopentadienes which could be Between sulfur and the PR fragment exists an isolobal relation. Meanwhile we are able to make accessible heterocycles of the type [T61-PR:-PR2r9-101. Since the [R2PS]-and [R$PPR2]-systems exhibit similar structural features, we were interested in the question whether the phosphorus analog also displays alkyne-like properties. In principle, an alkyne may be inserted into the Mo-PR:, Mo-PR2 or intothe R&P-PR2 bond of the above-mentioned three-membered heterocycle. In a communication["] lately we reported on the insertion of dimethyl acetylenedicarboxylate into the P-P bond o...

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Darstellung, Eigenschaften sowie Reaktionen metallhaltiger Heterocyclen. LXVI. Nickelinduzierte Cyclocodimerisierung eines Thioxophosphor(V)‐Kations mit einem aktivierten Alkin

Cited by 9 publications

References 26 publications

Air-Stable Phosphine Sulfide Ligand Precursors for Nickel-Catalyzed Cross-Coupling Reactions of Unactivated Aryl Chlorides with Aryl Grignard Reagents

Air-Stable Phosphine Sulfide Ligand Precursors for Nickel-Catalyzed Cross-Coupling Reactions of Unactivated Aryl Chlorides with Aryl Grignard Reagents

Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LXXVII Synthese, Struktur und Reaktivität von Phosphametallacyclopropanen mit isolobalen ER‐ (E = N, P, As, Sb) und Fe(CO)₄‐Bausteinen

Preparation, Properties, and Reactions of Metal‐Containing Heterocycles, XCI. Insertion of Activated Alkynes and Sulfur into the P‐P Bond of Diphosphamolybdacyclopropanes

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Darstellung, Eigenschaften sowie Reaktionen metallhaltiger Heterocyclen. LXVI. Nickelinduzierte Cyclocodimerisierung eines Thioxophosphor(V)‐Kations mit einem aktivierten Alkin

Cited by 9 publications

References 26 publications

Air-Stable Phosphine Sulfide Ligand Precursors for Nickel-Catalyzed Cross-Coupling Reactions of Unactivated Aryl Chlorides with Aryl Grignard Reagents

Air-Stable Phosphine Sulfide Ligand Precursors for Nickel-Catalyzed Cross-Coupling Reactions of Unactivated Aryl Chlorides with Aryl Grignard Reagents

Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LXXVII Synthese, Struktur und Reaktivität von Phosphametallacyclopropanen mit isolobalen ER‐ (E = N, P, As, Sb) und Fe(CO)4‐Bausteinen

Preparation, Properties, and Reactions of Metal‐Containing Heterocycles, XCI. Insertion of Activated Alkynes and Sulfur into the P‐P Bond of Diphosphamolybdacyclopropanes

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Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LXXVII Synthese, Struktur und Reaktivität von Phosphametallacyclopropanen mit isolobalen ER‐ (E = N, P, As, Sb) und Fe(CO)₄‐Bausteinen