403815-19-0

Basic information

• Product Name: 1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene
• Synonyms: 1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene
• CAS NO: 403815-19-0
• Molecular Weight: 1034.96
• Mol File: 403815-19-0.mol

Chemical Properties

• CAS DataBase Reference: 1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene(CAS DataBase Reference)
• NIST Chemistry Reference: 1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene(403815-19-0)
• EPA Substance Registry System: 1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene(403815-19-0)

Safety Data

• Hazardous Substances Data: 403815-19-0(Hazardous Substances Data)

Usage

Reaction

Ligand/palladium complex used in the direct arylation of heteroaromatic compounds with congested, functionalized aryl bromides. Suzuki-Miyaura Coupling of Aryl Bromides and Chlorides bearing alkyl, methoxy, keto, nitrile, etc. substitution to phenyl- and methoxybenzene boronic acids at Low Palladium Loading. Heck Coupling of Functionalized Aryl Bromides to n-butyl acrylate, styrene and n-butyl vinyl ether at Low Palladium Loading. Additional catalyzed reaction include Allylic Amination of Monoterpene Derivatives including geranylacetate, nerylacetate, linalylacetate and perillylacetate at Low Palladium Loading, and Sonogashira Cross-Coupling of Aryl Bromides by using stabilizing new copper-tetraphosphane adducts.

Upstream product

• 878190-70-6 [(bis(5-methyl-2-furyl)phosphino)cyclopentadienyl]lithium 
• 83272-80-4 lithium diphenylphosphinocyclopentadienyl 

Downstream Products

• 460049-14-3 Fe((CH₃)3CC₅H₂(P(C₆H₅)2)2)2Mo(CO)3 
• 403815-24-7 Fe(C₅H₂C(CH₃)3(P(C₆H₅)2)2)2RhClCO 
• 403815-25-8 Fe(C₅H₂C(CH₃)3(P(C₆H₅)2)2)2Rh(CO)2⁽¹⁺⁾*RhCl₂(CO)2^(1-)=Fe(C₅H₂C(CH₃)3(P(C₆H₅)2)2)2Rh(CO)2RhCl₂(CO)2 
• 403815-23-6 Fe(C₅H₂C(CH₃)3(P(C₆H₅)2)2)2Rh(CO)2⁽¹⁺⁾*BF₄^(1-)=Fe(C₅H₂C(CH₃)3(P(C₆H₅)2)2)2Rh(CO)2BF₄ 
• 460049-12-1 Fe((CH₃)3CC₅H₂(P(C₆H₅)2)2)2Cr(CO)3 
• 623946-94-1 Fe(C₅H₂C(CH₃)3(P(C₆H₅)2)2)2PdCl₂ 
• 623946-94-1 [PdCl₂(1,1',2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene)] 
• 769131-49-9 [NiBr₂(1,1',2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene)] 
• 769131-45-5 [NiCl₂(1,1',2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene)] 
• 1011480-81-1 [PdBr₂(1,1'2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene)] 
• 67675-73-4 catena[(μ3-iodo)(acetonitrile-N)copper(I)] 
• 1016567-35-3 P,P',P''-[1,1',2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene]iodocopper(I) 
• 1016567-40-0 P,P',P''-[1,1',2,3'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene]iodocopper(I) 

Relevant articles and documents

A sterically congested 1,2-diphosphino-1′-boryl-ferrocene: Synthesis, characterization and coordination to platinum

A new class of tritopic ferrocene-based ambiphilic compounds has been prepared by assembling diphosphino- and boryl-substituted cyclopentadienides at iron. The presence of five sterically demanding substituents on the ferrocene platform induces conformational constraints, as is apparent from XRD and NMR data, but does not prevent the chelating coordination to platinum. The Lewis acid moiety is pendant in both the free ligand and the platinum complex.

Functionalized tri- and tetraphosphine ligands as a general approach for controlled implantation of phosphorus donors with a high local density in immobilized molecular catalysts

Supported phosphine ligands are auxiliaries of topical academic and industrial interest in catalysis promoted by transition metals. However, both controlled implantation and controlled conformation of ligands should be achieved to produce immobilized catalysts that are able to structurally "copy" efficient homogeneous systems. We provide herein a general synthetic strategy for assembling a new class of branched tetraand triphosphine ligands with a unique controlled rigid conformation, and thus providing a high local density of phosphorus atoms for extended coordination to the metal center. We prepared new functionalized cyclopentadienyl (Cp) salts to design polyphosphines that were "ready for immobilization". These protected Cp fragments might also be of synthetic utility for generating other supported metallocenes. Tetra- and triphosphines were then formed and diversely functionalized for immobilization on virtually any kind of support. As evidenced by 31P NMR spectroscopy and the strong "through-space" spin- spin TSJ(P,P) coupling observed between P atoms, these modified polyphosphines induce, when immobilized on a support, a high local concentration of phosphorus donors that are spatially very close to each other (3-5 A?). These functionalized ligands have been incorporated into polystyrene to give either soluble or insoluble polymers and on inorganic supports such as silica. We report the catalytic performance at 0.05-0.5 mol% low palladium loading of the resulting immobilized polyphosphine ligands. This study provides proof-of-concept of supported catalytic materials built from modular polyphosphines with a novel approach to structurally controlled polydentate heterogeneous catalysts.

Conformational control of metallocene backbone by cyclopentadienyl ring substitution: A new concept in polyphosphane ligands evidenced by "through-space" nuclear spin-spin coupling. Application in heteroaromatics arylation by direct C-H activation

The present study deals with the conformational control of the metallocene backbone within ferrocenyl polyphosphane ligands and their performance in the highly topical palladium-catalyzed heteroaromatics arylation by direct C-H activation. New substituted

Through-space 31P spin-spin couplings in ferrocenyl tetraphosphine coordination complexes: Improvement in the determination of the distance dependence of JPP constants

From the analysis of several nickel and palladium halide complexes of a constrained ferrocenyl tetraphosphine, the existence in solution phase of unique 31P-31P through-space nuclear spin-spin coupling constants (JPP) had been previously evidenced. Due to the blocked conformation of the species in solution, and based on the NMR spectra obtained for the complexes and their corresponding solid state X-ray structures, these JPP constants had been shown to clearly depend on the mutual spatial position of the corresponding phosphorus atoms. Herein, the quantitative correlation disclosed at that time (P?P distance dependence of coupling constants) is remarkably confirmed, and mathematically refined owing to the study of a new palladium dibromide tetraphosphine complex, for which the synthesis and the solution NMR and solid state X-ray characterizations are reported.

First copper(I) ferrocenyltetraphosphine complexes: Possible involvement in Sonogashira cross-coupling reaction?

Preparation and characterization of the first examples of copper(I) ferrocenylpolyphosphine complexes are reported. The molecular structure of complex {P,P′,P″-[1,1′,2,2′-tetrakis(diphenylphosphino)- 4,4′-di-tert-butylferrocene]iodocopper(I)} (1) was solved by X-ray diffraction studies, and its fluxional behavior in solution was investigated by VT-31P NMR; both revealed a net triligated coordination preference of the ferrocenyl tetraphosphine Fc(P)4tBu with copper. The tetradentate ligand is an active auxiliary in Sonogashira alkynylation; therefore the general question of copper as a competitive coordination partner in the Pd/Cu-catalyzed Sonogashira reaction was raised and discussed. Electronically neutral, activated, and deactivated aryl bromides were employed for coupling with phenylacetylene with various [(Pd)/(Cu)/(tetraphosphine)] systems. The catalytic investigations shown that 1 mol % of complex 1 in combination with palladium is far more effective and selective for Sonogashira coupling than 5 mol % of CuI and palladium in the coupling to phenylacetylene of the deactivated aryl bromide 4-bromoanisole. This system efficiently avoids the concurrent and deleterious consumption of phenylacetylene by formation of diyne or enynes. To our knowledge, this is the first time that this kind of high selectivity is induced in Sonogashira alkynylation by initial ligand complexation to copper instead of palladium. These results demonstrate that coordination of Cu halide cocatalyst is a factor that should no longer be neglected in mechanistic and applied studies of the Sonogashira reaction.

General route to dissymmetric heteroannular-functionalized ferrocenyl 1,2-diphosphines: Selective synthesis and characterization of a new class of tri- and tetrasubstituted ferrocenyl compounds

Several monosubstituted-cyclopentadienyl anions (A-Li) and [1,2-bis(diphenylphosphino)-4-tert-butylcyclopentadienyl]lithium (B-Li) react with FeCl2 to afford a novel class of multidentate ferrocenylphosphines (A-Fe-B). The proposed synthetic method represents a unique means to produce achiral dissymmetric 1,1′,2-substituted ferrocenes (A-Fe-B) bearing a heteroannular 1′-substituent which is different from the homoannular 1- and 2-substituents. The selectivity for the two-step reaction favors formation of the desired dissymmetric product (A-Fe-B) rather than the concurrent formation of the symmetric di- and tetrasubstituted ferrocenes (A-Fe-A and B-Fe-B). Therefore, this method allows access to a great number of dissymmetric multidentate metalloligands, especially when one considers that functionalized-Cp salts continue to expand in terms of number and diversity. Herein, emphasis was placed upon the 1H, 13C, and 31P NMR characterization of the metalloligands; several examples exhibit intriguing conformational properties and rare through-space phosphorus nuclear-spin couplings.

1,1′,2,2′-Tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene, a new cisoid arrangement of phosphino groups

The action of two equivalents of 1,2-bis(diphenylphosphino)-4-tert-butylcyclopentadienyllithium on FeCl2 led to the corresponding 1,1′,2,2′-tetraphosphinoferrocene. The X-ray structure of this bulky ferrocene is described. The spectroscopic results reveal a conformational chirality with a cisoid disposition of the phosphino groups. The first results about the complexation with representative elements of Group IX and X (Rh, Pd, Ir) are reported.