The syntheses and structures of iron carbonyl adducts of tricoordinated hypervalent phosphorus compounds

Arduengo, Anthony J.; Lattman, Michael; Dixon, David A.; Calabrese, Joseph C.

doi:10.1002/hc.520020307

Cited by 11 publications

(17 citation statements)

References 43 publications

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“…The iron carbonyl slowly dissolves to give ADPO-Fe(CO)4 in quantitative yield (eq 25). 63 This same adduct has also been formed by the reaction of ADPO-Cl2 with Na2[Fe(CO)4]2.63 The IR spectrum of ADPO-Fe (CO)4 shows the typical vco for an axially substituted LFe(CO)4.65 However, the bands are at a higher frequency compared to other LFe(CO)4 (L = alkylgP,66 Ph^P,66 (Me2N)3P67) and even higherthan for (MeO)3PFe(CO)4,66whichsuggeststhat folded ADPO is a good x-acceptor. The 'H NMR shift of the ring protons exhibit the expected upfield shift (6 7,50 -*• 5.89) with the corresponding increase in 3Jph (9.6 Hz -* 26.4 Hz) when going from free ADPO to a complexed, folded 8-P-4 ADPO structure.…”

Section: Transition Metal Complexesmentioning

confidence: 99%

Low coordinate hypervalent phosphorus

Arduengo¹,

Stewart²

1994

Chem. Rev.

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140

122

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A. Complexes with the Transition Group 6 1230 Metals, Cr and W B. Complexes with the Transition Group 7 1230 Metal, Mn C. Complexes with the Transition Group 8 1231 Metals, Fe and Ru D. Complexes with the Transition Group 10 1232 Metals, Ni, Pd, and Pt E. Complexes with the Transition Group 11 1234 Metal, Ag X. Conclusions 1235 XI. Abbreviations 1236 XII. References 1236 I. Introduction This review marks 10 years of research into the chemistry of low-coordinate hypervalent phosphorus compounds.1 The first tricoordinated hypervalent phosphorus compound, 10-P-323,7-di(tert-butyl)-5-aza-2,8dioxa-l-phosphabicyclo[3.3.0]octa-2I4,6-triene (AD-PO),3 was reported in 1983.4 Another type of 10-P-3 intermediate, 1, was discovered by Schmid peter and Lochschmidt in this same time frame.5 The work by Schmidpeter et al. and Arduengo et al. represent two different ligand designs to stabilize the 11n memory of Linus Amadeus and Schroeder. * Contribution no. 6745 from DuPont Science and Engineering Laboratory. * DuPont. I Himont. Anthony J. Arduengo, III (b 1952) was raised In Atlanta, GA. He received the Bachelor of Science degree (with honor) in chemistry from The Georgia Institute of Technology (1974) and Ph.D. in organic chemistry from the same Institution in 1976. After a year In Industry with DuPont's Central Research Department, he joined the organic chemistry faculty of The University of Illinois-Urbana. In 1984 he returned to DuPont where he has held various positions and Is currently a Research Leader in the Polymer Science Section of the Central Science and Engineering Laboratory. He has served on the editorial boards of Chemical Reviews and Heteroatom Chemistry as well as the IUPAC commission on Inorganic nomenclature. His research interests are broadly in the area of main group element chemistry with particular interest in compounds with unusual valence. Hobbies include trumpet playing, bicycling, antique cars, and classical music. Constantine A. Stewart was born in 1957 in San Angelo, TX. He received his Bachelor of Arts in chemistry (1980) from Texas Tech University in Lubbock, TX, and his Ph.D. in inorganic chemistry from the University of Texas at Austin (1984). He spent two years as a Visiting Research Scientist at Central Research and Development at DuPont. In 1986 he joined Himont U.S.A., Research and Development. He is currently working In the field of Ziegler-Natta catalysis. His hobbies include bicycling and photography.T-shaped 10-P-3 geometry. Both designs employ a bicyclic five-membered ring effect to stabilize an axialequatorial-axial chelation of the central pseudo-trigonal

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Section: Transition Metal Complexesmentioning

confidence: 99%

Low coordinate hypervalent phosphorus

Arduengo¹,

Stewart²

1994

Chem. Rev.

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140

122

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“…Dimerization of the phosphine by cleavage of one of the five-membered rings and formationo fanew ten-membered heterocycle resulted upon treatment of four equivalents of 1a with Pd 2 + cations {[Pd(NCMe) 4 ] 2 + }. [37] Additiono ft he chelating tetradentatel igand [Ph 2 PCH 2 CH 2 P(Ph)CH 2 ] 2 to the isolateda nd characterized palladium complex resulted in the release of the dimer (36). [37] A similar dimerization was observed upon irradiationo fa ni ntermediate [Fe(CO) 3 L 2 ]c omplex (L = 1a).…”

Section: Transition-metal Complexesmentioning

confidence: 82%

“…Schematic drawings of those compounds ( 30 to 34 ), which have been characterized by crystal structure determination, are depicted in Figure . In the structure of 31 , the phosphorus atom occupied an axial position of the trigonal‐bipyramidal coordination sphere of iron, and the ligand adopted a folded geometry . A comparatively short Fe−P distance was interpreted in terms of a strong π‐acceptor capability of the ligand, and the isomer with a planar ligand was calculated to be only slightly higher in energy .…”

Section: Reactivitymentioning

confidence: 99%

“…[36] Ac omparatively short FeÀPd istance was interpreted in terms of as trong p-acceptor capability of the ligand, and the isomer with ap lanar ligand was calculated to be only slightly higheri ne nergy. [36] Compounds 32 [37] and 33 [38] have the homoleptic coordinationo f the metal atoms with four ligandsi natetrahedral (32)o ra n unusualp lanar arrangement ( 33). Thef ormation of the silver compounds 33 [38] and 34 [39] depends on the stoichiometric ratio of the reactants.…”

Section: Transition-metal Complexesmentioning

confidence: 99%

“…In the structure of 31 , the phosphorus atom occupied an axial position of the trigonal‐bipyramidal coordination sphere of iron, and the ligand adopted a folded geometry . A comparatively short Fe−P distance was interpreted in terms of a strong π‐acceptor capability of the ligand, and the isomer with a planar ligand was calculated to be only slightly higher in energy . Compounds 32 and 33 have the homoleptic coordination of the metal atoms with four ligands in a tetrahedral ( 32 ) or an unusual planar arrangement ( 33 ).…”

Section: Reactivitymentioning

confidence: 99%

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Sterically Constrained Bicyclic Phosphines: A Class of Fascinating Compounds Suitable for Application in Small Molecule Activation and Coordination Chemistry

Brand

Uhl

2018

Chemistry A European J

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Bicyclic phosphines with two annulated, electronically unsaturated five-membered heterocycles are available through facile routes. In most cases, their phosphorus atoms are bound to heteroatoms such as oxygen or nitrogen (PN or PN O), whereas homoleptic coordination by three sp -hybridized carbon atoms has been reported only recently. Steric strain causes unique reactivity. Oxidative addition of halogens, N-H or O-H bonds have afforded phosphoranes as valuable materials for secondary processes. Ring opening was identified as an important step for the understanding of these reactions and has been observed experimentally with a diphosphorus-based ring system. A PH derivative has been considered as a model system for small molecule activation, and hydrogen transfer to a diazo compound was observed experimentally. Several of these phosphines are excellent ligands for the coordination of transition-metal atoms. The very bulky PC compound has a basicity similar to that of PPh and may allow the synthesis of complexes with unusually low coordination numbers at the metal atoms. These phosphines found recently renewed interest as promising reagents in various secondary transformations such as the activation of σ-bonds or in coordination chemistry.

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Verbindungen mit planar tetrakoordiniertem Kohlenstoff

Röttger¹,

Erker²

1997

Angewandte Chemie

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Es ist eine große Herausforderung, Verbindungen mit planar tetrakoordiniertem Kohlenstoff zu synthetisieren, die so stabil sind, daß man sie isolieren und bei Normalbedingungen untersuchen und handhaben kann. Deshalb hat es viele Versuche gegeben, Kohlenwasserstoffgerüste so zu konstruieren, daß sie das tetrakoordinierte Kohlenstoffatom in seiner nichtnatürlichen planaren Koordinationsgeometrie aufnehmen und z. B. durch sterischen Zwang stabil halten könnten. Viel leichter kommt man offenbar zum Ziel, wenn man quadratisch‐planar umgebene Kohlenstoffatome elektronisch stabilisiert. Planar tetrakoordinierte Kohlenstoffatome sind sp2‐hybridisiert und durch ein Elektronenmangel‐σ‐System charakterisiert. Das zur σ‐Bindungsebene orthogonale p‐Orbital ist mit zwei Elektronen besetzt. Daher sind σ‐Donor/π‐Acceptorsubstituenten, und damit viele Metalle, prinzipiell in der Lage, diese nichtnatürliche Koordinationsgeometrie des tetrakoordinierten Kohlenstoffatoms elektronisch zu stabilisieren. Mittlerweile gibt es gut ausgearbeitete Wege zu sehr stabilen „Anti‐van't Hoff/Le Bel‐Verbindungen”︁, bei denen ein planar tetrakoordiniertes Kohlenstoffatom meist durch die gemeinsame Wirkung von zwei direkt gebundenen Metallatomen stabilisiert wird. Das „quadratisch‐planar”︁ umgebene Kohlenstoffatom ist dabei oft Teil eines Doppelbindungssystems. Typische stabilisierende Metallkombinationen sind Zirconium und Aluminium oder Zirconium und Bor. Aber es gibt auch Beispiele mit zwei Übergangsmetallen von der rechten Seite des Periodensystems. Darüber hinaus liegen mittlerweile verläßliche Abschätzungen zur Stabilisierung der planaren Tetrakoordination in solchen Verbindungen vor. Aus theoretischen und experimentellen Untersuchungen ergibt sich, daß in Zr/Zr+‐oder Zr/Al‐Verbindungen die planare Tetrakoordination des Kohlenstoffatoms ca. 12 bzw. 40 kcal mol−1 günstiger ist als die trigonal‐planare Koordination. Quadratisch‐planar koordinierter Kohlenstoff ist damit in Organometallverbindungen kein ungewöhnliches Strukturmerkmal mehr und muß häufiger als bisher als eine alternative strukturelle Möglichkeit in Betracht gezogen werden.

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The syntheses and structures of iron carbonyl adducts of tricoordinated hypervalent phosphorus compounds

Abstract: The hypemalent phosphorus compound 3,7-di-tbutyl-

Cited by 11 publications

References 43 publications

Low coordinate hypervalent phosphorus

Low coordinate hypervalent phosphorus

Sterically Constrained Bicyclic Phosphines: A Class of Fascinating Compounds Suitable for Application in Small Molecule Activation and Coordination Chemistry

Verbindungen mit planar tetrakoordiniertem Kohlenstoff

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