Novel Rh<sup>I</sup> Piano‐Stool Complexes with New Hemilabile Ligands Ligating through Phosphane and Arene Groups: Synthesis, Characterization, and Reactivity

Singewald, Elizabeth T.; Mirkin, Chad A.; Levy, Allison; Stern, Charlotte L.

doi:10.1002/anie.199424731

Cited by 31 publications

(31 citation statements)

References 12 publications

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“…The same reaction products are obtained upon treatment of the rhodium(I) precursor of IV with CO or isocyanide. This reaction, however, is much slower (20,22). This finding can be explained.…”

Section: B the P-arene-phosphine Rh(ii) Complexesmentioning

confidence: 62%

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The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

Bruin

Hetterscheid

Koekkoek

et al. 2007

Progress in Inorganic Chemistry

121

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Section: B the P-arene-phosphine Rh(ii) Complexesmentioning

confidence: 62%

“…9) has been described in detail (19)(20)(21)(22). The relative kinetic and thermodynamic stabilities of these complexes were investigated by electrochemical methods.…”

Section: B the P-arene-phosphine Rh(ii) Complexesmentioning

confidence: 99%

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

Bruin

Hetterscheid

Koekkoek

et al. 2007

Progress in Inorganic Chemistry

121

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“…Our group has introduced and focused on developing one of these strategies, which is referred to as the Weak-Link Approach (Scheme 1). This strategy allows one to prepare bimetallic macrocycles from simple transition metal and ligand precursors (7)(8)(9)(10)(11)(12), and it is based on reactions between flexible symmetrical hemilable ligands (13)(14)(15)(16) and transition metal precursors. Typically, macrocyclic intermediates that contain both strong (S-M) and weak (W-M) ligand-metal bonds (Scheme 1) are initially formed in very high and usually quantitative yield.…”

mentioning

confidence: 99%

Threefold symmetric trimetallic macrocycles formed via the Weak-Link Approach

Ovchinnikov

Holliday

Mirkin

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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The synthesis and characterization of a new threefold symmetric hemilabile phosphino-alkylthioether ligand are described. This ligand can be used in combination with Rh(I) and Ir(I) precursor complexes to prepare 40-membered macrocyles with threefold symmetry via the Weak-Link Approach. Synthesis and characterization of two such structures are reported along with a single crystal x-ray diffraction analysis of one of the key intermediates in the case of Rh(I). This is a demonstration of the viability of the Weak-Link Approach for preparing structures other than bimetallic macrocycles and suggests that it could be generalized for a wide range of higher symmetry structures through appropriate hemilabile ligand design. R ecent developments in the field of supramolecular chemistry have resulted in the establishment of several new synthetic strategies for forming multimetallic macrocyclic architectures (1-6). Our group has introduced and focused on developing one of these strategies, which is referred to as the Weak-Link Approach (Scheme 1). This strategy allows one to prepare bimetallic macrocycles from simple transition metal and ligand precursors (7-12), and it is based on reactions between flexible symmetrical hemilable ligands (13-16) and transition metal precursors. Typically, macrocyclic intermediates that contain both strong (S-M) and weak (W-M) ligand-metal bonds (Scheme 1) are initially formed in very high and usually quantitative yield. For the systems studied thus far, ligands that consist of flexible phosphinoalkyl ether (7), thioether (12), or amino (11) bidentate ligand functionalities connected with rigid aromatic spacers (R) have been used. Once condensed, macrocyclic intermediates are formed, the weak ligand-metal bonds in these intermediates can be cleaved by means of simple ligand substitution reactions to afford open macrocyclic ring structures. Alternatively, both condensed and opened macrocycles can be used to construct more complex three-dimensional architectures such as cylinders (8) and trilayer metallocyclophanes (9).Although the generality of the weak-link methodology has been demonstrated with respect to twofold symmetric hemilabile ligands and transition metals, the application of this synthetic approach to the preparation of macrocyclic structures with more than two metals has not been demonstrated. Herein, we report the first application of the Weak-Link Approach to the formation of trimetallic (17-20) rhodium and iridium macrocycles from a flexible threefold symmetric hemilabile ligand. Methods and MaterialsGeneral Procedures. All reactions were performed under a nitrogen atmosphere in reagent grade solvents by using standard Schlenk or dry-box techniques (21). All other solvents were purified by published methods (22,23). Chemicals were purchased from Aldrich, unless otherwise mentioned, or prepared by literature methods, as referenced below.

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“…Diphenyl(3-phenylpropyl)phosphine, (I), is a potentially chelating ligand that has been prepared by several groups for the study of tethered arene-Rh I and Ru II complexes of the type [Rh{η 1 -Ph 2 P(CH 2 ) 3 C 6 H 5 }{η 1 :η 6 -Ph 2 P(CH 2 ) 3 C 6 H 5 }] (Singewald et al, 1994(Singewald et al, , 1996 and [RuCl 2 {η 1 :η 6 -Ph 2 P(CH 2 ) 3 C 6 H 5 }] Ghebreyessus & Nelson, 2000;Smith & Wright, 1998). (I) may coordinate to the metal centre through both the phosphorus donor atom and the alkyl arene.…”

Section: S1 Commentmentioning

confidence: 99%

Diphenyl(3-phenylpropyl)phosphine

et al. 2001

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Novel Rh^I Piano‐Stool Complexes with New Hemilabile Ligands Ligating through Phosphane and Arene Groups: Synthesis, Characterization, and Reactivity

Cited by 31 publications

References 12 publications

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

Threefold symmetric trimetallic macrocycles formed via the Weak-Link Approach

Diphenyl(3-phenylpropyl)phosphine

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Novel RhI Piano‐Stool Complexes with New Hemilabile Ligands Ligating through Phosphane and Arene Groups: Synthesis, Characterization, and Reactivity

Cited by 31 publications

References 12 publications

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

Threefold symmetric trimetallic macrocycles formed via the Weak-Link Approach

Diphenyl(3-phenylpropyl)phosphine

Contact Info

Product

Resources

About

Novel Rh^I Piano‐Stool Complexes with New Hemilabile Ligands Ligating through Phosphane and Arene Groups: Synthesis, Characterization, and Reactivity