Structural characterisation of an acetylenic diphosphine derivative of π-cyclopentadienyliron dicarbonyl dimer: an unusual Mössbauer effect

Carty, Arthur J.; Ng, T. W.; Carter, W.; Palenik, Gus J.; Birchall, T.

doi:10.1039/c29690001101

Cited by 23 publications

(8 citation statements)

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“…Binuclear cyclopentadienyliron carbonyls have been known since the 1950s. Table gives experimentally derived Fe–Fe bond distances in complexes 01 to 09 which span a wide structural variety. − Complexes 01 to 08 have Fe–Fe bond lengths from 2.49 to 2.59 Å which are consistent with single bonds. Complexes 06 and 07 are trans and cis isomers of the doubly bridged tetracarbonyl Cp 2 Fe 2 (CO) 2 (μ-CO) 2 with very similar Fe–Fe single bond lengths and coexisting in equilibrium in solution. , A crystal structure study (Mitschler, Rees, and Lehmann) of Cp 2 Fe 2 (CO) 2 (μ-CO) 2 gave an Fe–Fe bond distance of 2.539 Å.…”

Section: Iron–iron Bondsmentioning

confidence: 91%

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

2018

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This survey of metal–metal (MM) bond distances in binuclear complexes of the first row 3d-block elements reviews experimental and computational research on a wide range of such systems. The metals surveyed are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, representing the only comprehensive presentation of such results to date. Factors impacting MM bond lengths that are discussed here include (a) the formal MM bond order, (b) size of the metal ion present in the bimetallic core (M2) n+, (c) the metal oxidation state, (d) effects of ligand basicity, coordination mode and number, and (e) steric effects of bulky ligands. Correlations between experimental and computational findings are examined wherever possible, often yielding good agreement for MM bond lengths. The formal bond order provides a key basis for assessing experimental and computationally derived MM bond lengths. The effects of change in the metal upon MM bond length ranges in binuclear complexes suggest trends for single, double, triple, and quadruple MM bonds which are related to the available information on metal atomic radii. It emerges that while specific factors for a limited range of complexes are found to have their expected impact in many cases, the assessment of the net effect of these factors is challenging. The combination of experimental and computational results leads us to propose for the first time the ranges and “best” estimates for MM bond distances of all types (Ti–Ti through Zn–Zn, single through quintuple).

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Section: Iron–iron Bondsmentioning

confidence: 91%

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

2018

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“…Although an early example was the regulation of glycogen phosphorylase by a phosphopeptides mimic of the N-terminus of that protein, 33 the interpretation of that data has now been questioned. 34 Therefore, other examples will be considered.…”

Section: Example Of Peptide Mimics Of Order-disorder Elements In the mentioning

confidence: 99%

Are all regions of folded proteins that undergo ligand‐dependent order–disorder transitions targets for allosteric peptide mimetics?

Fenton

2013

Biopolymers

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Although the classical view of how proteins function relied on well folded structures, it is now recognized that the function of many proteins is dependent on being intrinsically disordered. The primary consideration in this work is the intermediate group of proteins that are overall well folded, but which contain small regions that undergo order/disorder transitions. In particular, the current focus is on those order/disorder transitions that are energetically coupled to ligand binding. As exemplified by the case of human liver pyruvate kinase (hL-PYK), peptides that mimic the sequence of the order/disorder region can be used as allosteric regulators of the enzyme. Based on this example and others reported in the literature, we propose that a similar use of peptides that mimic protein regions that experience ligand-dependent order-disorder transitions can be a generalized initiation point for the development of allosteric drugs.

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“…In the square-planar complex m-PdCl2[Ph2PC=CCF3]2 (I) and the platinum analog (II) (vide infra) the alkyne triple bonds are uncoordinated yet are held proximate to the coordination sphere of the metal and to one another. [1][2][3][4][5] The phosphorus-coordinated phosphinoacetylenes in these derivatives are activated and highly susceptible to nucleophilic attack at phosphorus or an alkyne carbon atom. These reactions have provided synthetic routes to the stabilized coordinated ligands [R2PO-H-OPR2]-and R2POH via nucleophilic displacement at phosphorus,6*7 to R2PCH=C-(CF2)0 chelates and /3-keto phosphines via acetylene hydration,7 and to unsymmetrical diphosphines via base-promoted acetylene coupling8 or R2PH addition.9 The apparent analogy of acetylene coupling in the formation of m-MCh-(Ph2PCH2C(CF3)CHPPh2) (M = Pd, Pt) from I and II to the dimerization of adjacent alkyne groups in o-bis(phenylethynyl)benzene promoted by both electrophilic and nucleophilic reagents10 together with the known1 b12 susceptibility of alkynes to electrophilic attack prompted us to investigate the addition of hydrogen chloride to I and II.…”

Section: Introductionmentioning

confidence: 99%

Reactions of acetylenes held proximate to a metal. Addition of hydrogen chloride to cis-dichlorobis(3,3,3-trifluoropropynyldiphenylphosphine)palladium(II) and -platinum(II). The x-ray structure of trans-PdCl2[Ph2PCH:C(Cl)CF3]2

Taylor¹,

Jacobson²,

Carty³

1975

Inorg. Chem.

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Structural characterisation of an acetylenic diphosphine derivative of π-cyclopentadienyliron dicarbonyl dimer: an unusual Mössbauer effect

Cited by 23 publications

References 0 publications

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

Are all regions of folded proteins that undergo ligand‐dependent order–disorder transitions targets for allosteric peptide mimetics?

Reactions of acetylenes held proximate to a metal. Addition of hydrogen chloride to cis-dichlorobis(3,3,3-trifluoropropynyldiphenylphosphine)palladium(II) and -platinum(II). The x-ray structure of trans-PdCl2[Ph2PCH:C(Cl)CF3]2

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