(Bis{2,4,6-triisopropylphenyl}stannylene)ferrocenophane and Related Ring-Opened Products

Sharma, Hemant; Cervantes‐Lee, Francisco; Mahmoud, Jawad S.; Pannell, Keith H.

doi:10.1021/om9805234

Cited by 73 publications

(35 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[a] [40] Sn(C 6 H 2 iPr 3 ) 2 14.7 [41] SntBu 2 14.1(2) [42] SnMes 2 14.5(2), 15.3(2), and 15.7(3) [b] [ 43] [a] The digermanium-bridged compound has a smaller tilt angle than the CH 2 CH 2 -and SiMe 3 SiMe 3 -bridged FCPs, as expected. It is resistant against both thermal and anionic ROP.…”

mentioning

confidence: 68%

Polyferrocenylsilane‐Based Polymer Systems

Bellas¹,

Rehahn²

2007

Angew Chem Int Ed

290

207

View full text Add to dashboard Cite

The study of metallopolymers has blossomed into a mature field over the last few decades. Especially, polyferrocenylsilane (PFS) chemistry has taken a tremendous leap and continues to raise intense interest. Since the discovery of thermal ring-opening polymerization (ROP) of sila[1]ferrocenophanes, PFSs have been also accessed by anionic, cationic, transition-metal-catalyzed, and photolytic anionic ROP methodologies. A plethora of synthetic strategies have been devised, enabling access to a wide variety of copolymers, polyelectrolytes, and nanostructured materials. The distinctive physical properties and functions of many PFS-based polymers have been explored, leading to their apt exploitation in technical applications. Therefore, it is conceivable that PFS-related platforms might be indispensable nano-objects in the near future, as they stand on the verge of a new generation of sophisticated materials.

show abstract

mentioning

confidence: 68%

Polyferrocenylsilane‐Based Polymer Systems

Bellas¹,

Rehahn²

2007

Angew Chem Int Ed

290

207

View full text Add to dashboard Cite

show abstract

“…In all cases to date, the stability of stanna [1]ferrocenophanes is owed to sterically imposing substituents on the tin atom (e.g. tBu, [27] 2,4,6-trimethylphenyl, [27] 2,4,6-triisopropylphenyl [99] ). For example, the reaction of dilithioferrocene(tmeda) and diorganodichlorostannanes R 2 SnCl 2 produces only oligomeric products (M n < 4600; for R = Me, Et, nBu, Ph) and/or cyclic dimers (for R = Et, nBu).…”

Section: Ansa Complexesmentioning

confidence: 99%

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

2007

View full text Add to dashboard Cite

The structures, bonding, and ring-opening reactions of strained cyclic carbon-based molecules form a key component of standard textbooks. In contrast, the study of strained organometallic molecules containing transition metals is a much more recent development. A wealth of recent research has revealed fascinating nuances in terms of structure, bonding, and reactivity. Building on initial work on strained ferrocenophanes, a broad range of strained organometallic rings composed of a variety of different metals, pi-hydrocarbon ligands, and bridging elements has now been developed. Such strained species can potentially undergo ring-opening reactions to functionalize surfaces and ring-opening polymerization to form easily processed metallopolymers with properties determined by the presence of the metal and spacer. This Review summarizes the current state of knowledge on the preparation, structural characterization, electronic structure, and reactivity of strained organometallic rings with pi-hydrocarbon ligands and d-block metals.

show abstract

“…Since the discovery of the first example, sila [1]ferrocenophane 1 in 1975 by Osborne and co-workers, [1] strained [1]ferrocenophanes 2 have attracted considerable attention and have inspired growing interest in a range of related species containing various metals, [2][3][4][5][6][7][8][9][10][11] bridging elements [12][13][14][15][16][17][18][19][20][21][22][23][24][25] and even p-hydrocarbon ligands. [26][27][28][29][30][31][32][33][34][35] The angle created by the planes of the two Cp rings in a ferrocenophane, generally denoted as a, serves as a convenient qualitative measure of the degree of strain present.…”

Section: Introductionmentioning

confidence: 99%

Photoinduced FeCp Bond Cleavage and Insertion Reactions of Strained Silicon‐ and Sulphur‐Bridged [1]Ferrocenophanes in the Presence of Transition‐Metal Carbonyls

Ieong

Chan

Lough

et al. 2008

Chemistry A European J

View full text Add to dashboard Cite

The photochemical reactions of the moderately strained sila[1]ferrocenophane [Fe(eta-C(5)H(4))(2)SiPh(2)] (1) and the highly strained thia[1]ferrocenophane [Fe(eta-C(5)H(4))(2)S] (8) with transition-metal carbonyls ([Fe(CO)(5)], [Fe(2)(CO)(9)] and [Co(2)(CO)(8)]) have been studied. The use of metal carbonyls has allowed the products of photochemically induced Fe-cyclopentadienyl (Cp) bond cleavage reactions in the [1]ferrocenophanes to be trapped as stable, characterisable products. During the course of these studies the synthesis of 8 from [Fe(eta-C(5)H(4)Li)(2)TMEDA] (TMEDA=N,N,N',N'-tetramethylethylenediamine) and S(SO(2)Ph)(2) has been significantly improved by a change of reaction solvent and temperature. Photochemical reaction of 1 with excess [Fe(CO)(5)] in THF gave the dinuclear complex [Fe(2)(CO)(2)(mu-CO)(2)(eta-C(5)H(4))(2)SiPh(2)] (9). The analogous photolytic reaction of 8 with [Fe(CO)(5)] in THF gave cyclic dimer [Fe(eta-C(5)H(4))(2)S](2) (10) and [Fe(2)(CO)(2)(mu-CO)(2)(eta-C(5)H(4))(2)S] (11), with the former being the major product. Photolysis of 1 with [Co(2)(CO)(8)] afforded the remarkable tetrametallic dimer [(CO)(2)Co(eta-C(5)H(4))SiPh(2)(eta-C(5)H(4))Fe(CO)(2)](2) (13). The corresponding photochemical reaction of 8 with [Co(2)(CO)(8)] gave a trimetallic insertion product in high conversion, [Co(CO)(4)(CO)(2)Fe(eta-C(5)H(4))S(eta-C(5)H(4))Co(CO)(2)] (14). These reactivity studies show that UV light promotes Fe-Cp bond cleavage reactions of both of the [1]ferrocenophanes 1 and 8. We have found that, whereas the less strained sila[1]ferrocenophane 1 requires photoactivation for Fe-Cp bond insertions to occur, the highly strained thia[1]ferrocenophane 8 undergoes both irradiative and non-irradiative insertions, although the latter occur at a slower rate. Our results suggest that such photoinduced bond cleavage reactions may be general and applicable to other related strained organometallic rings with pi-hydrocarbon ligands.

show abstract

(Bis{2,4,6-triisopropylphenyl}stannylene)ferrocenophane and Related Ring-Opened Products

Cited by 73 publications

References 38 publications

Polyferrocenylsilane‐Based Polymer Systems

Polyferrocenylsilane‐Based Polymer Systems

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

Photoinduced FeCp Bond Cleavage and Insertion Reactions of Strained Silicon‐ and Sulphur‐Bridged [1]Ferrocenophanes in the Presence of Transition‐Metal Carbonyls

Contact Info

Product

Resources

About