Gyroscopes and the chemical literature: 1852–2002

Skopek, Katrin; Hershberger, Mark C.; Gladysz, J. A.

doi:10.1016/j.ccr.2006.12.015

Cited by 90 publications

(53 citation statements)

References 30 publications

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“…16,21 If the CO ligands were trans, only a single IR band would be expected. As shown in Scheme 2, the reference compound cis,cis,trans-Os(CO) 2 (Br) 2 (P(n-C 8 H 17 ) 3 ) 2 (8a) was isolated in 85% yield following the hydrogenation of the dibromide complex 3a. As given in Table 1, the ν CO values, 13 C NMR chemical shifts and J CP values, and 31 P NMR chemical shift were very close to those of 2a-c and 3a-c. As shown in Scheme 2, dilute chlorobenzene solutions of 2a-c and 3a-c (0.0010 M) were treated with Grubbs' first generation catalyst (7.0-7.5 mol%).…”

Section: Ring Closing Metatheses Of Octahedral Osmium(ii) Complexesmentioning

confidence: 99%

“…The IR ν CO bands of the starting materials were replaced by a single absorption at lower frequencies, indicative of enhanced backbonding. Workups gave the target complexes transOs(CO) 3 (P((CH 2 ) n ) 3 P) (9a,c) in 79-82% yields, and the phosphacycle containing species trans-Os(CO) 3 (P(CH 2 ) 15 CH 2 )((CH 2 ) 16 )(P(CH 2 ) 15 CH 2 ) (9′b) in 53-84% yields, all as white solids. A model complex with two acyclic trialkylphosphine ligands, cis,cis,trans-Os (CO) 3 (P(n-C 8 H 17 ) 3 ) 2 (10a), was similarly prepared in 85% yield from 8a (Scheme 2).…”

Section: Trigonal Bipyramidal Osmium(0) Complexesmentioning

confidence: 99%

“…However, they are accompanied by isomers derived from a mixed intra/interligand metathesis mode, which dominate in the case of n = 16. The chloride or bromide ligands in these octahedral systems undergo both substitution and reduction, with the latter affording (under CO atmospheres) trigonal bipyramidal gyroscope like complexes with Os(CO) 3 rotators. These can be protonated by acids HX to give octahedral cationic hydride complexes.…”

Section: Summary and Prospectivementioning

confidence: 99%

“…2 Although the term "gyroscope" has been applied rather loosely to molecules, 3 only a few investigators have been actively trying to engineer working devices. [4][5][6] A common denominator among these efforts has been the construction of cage like housings, often termed "stators", which shield the rotating moieties or "rotators" from their surroundings.…”

Section: Introductionmentioning

confidence: 99%

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Gyroscope like molecules consisting of trigonal or square planar osmium rotators within three-spoked dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties

et al. 2016

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aReactions of (NH 4 ) 2 OsX 6 (X = Cl, Br) with CO and the phosphines P((CH 2 ) m CHvCH 2 ) 3 (m = 6, a; 7, b; 8, c) give cis,cis,trans-Os(CO) 2 (X) 2 (P((CH 2 ) m CHvCH 2 ) 3 ) 2 (46-73%). These are treated with Grubbs' catalyst (7 mol%, 0.0010 M, C 6 H 5 Cl). Subsequent hydrogenations (PtO 2 ) yield the gyroscope like complexes cis,cis,trans-Os(CO) 2 (X) 2 (P((CH 2 ) n ) 3 P) (n = 2m + 2; X = Cl, 6a-c; Br, 7a-c; 5-31%) and the isomers cis,cis,trans-Os(CO) 2 (X) 2 (P(CH 2 ) n−1 CH 2 )((CH 2 ) n )(P(CH 2 ) n−1 CH 2 ) (X = Cl, 6'a-c; Br, 7'a-c; 12-51%) derived from a combination of interligand and intraligand metatheses. Reductions of 6a,c, 6'b, and 7'b with C 8 K under CO atmospheres afford trans-Os(CO) 3 (P((CH 2 ) n ) 3 P) (9a,c, 79-82%) and trans-

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Section: Ring Closing Metatheses Of Octahedral Osmium(ii) Complexesmentioning

confidence: 99%

Section: Trigonal Bipyramidal Osmium(0) Complexesmentioning

confidence: 99%

Section: Summary and Prospectivementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Gyroscope like molecules consisting of trigonal or square planar osmium rotators within three-spoked dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties

et al. 2016

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“…In the last few years the development of powerful synthetic methodologies, combined with a device-driven ingenuity evolved from the attention to functions and reactivity, have led to remarkable achievements in this field. Among the systems reported are molecular tweezers [9], propellers [10], rotors [11], turnstiles [12], gyroscopes [13,14], gears [15], brakes [16], a molecular pedal [17], ratchets [18], rotary motors [19], shuttles [20], elevators [21], muscles [22], valves [23], processive artificial enzymes [24], walkers [25][26][27], vehicles [28], and catalytic self-propelled micro-and nano-objects [29,30]. Several excellent reviews [31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] and a monograph [47] dealing with artificial molecular machines and motors are available.…”

Section: Introductionmentioning

confidence: 99%

Molecular machines operated by light

Venturi

2008

Open Chemistry

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Abstract:The bottom-up construction and operation of machines and motors of molecular size is a topic of great interest in nanoscience, and a fascinating challenge of nanotechnology. Researchers in this field are stimulated and inspired by the outstanding progress of molecular biology that has begun to reveal the secrets of the natural nanomachines which constitute the material base of life. Like their macroscopic counterparts, nanoscale machines need energy to operate. Most molecular motors of the biological world are fueled by chemical reactions, but research in the last fifteen years has demonstrated that light energy can be used to power nanomachines by exploiting photochemical processes in appropriately designed artificial systems. As a matter of fact, light excitation exhibits several advantages with regard to the operation of the machine, and can also be used to monitor its state through spectroscopic methods. In this review we will illustrate the design principles at the basis of photochemically driven molecular machines, and we will describe a few examples based on rotaxane-type structures investigated in our laboratories. © Versita Warsaw and Springer-Verlag Berlin

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Self‐Assembly of Coordination Compounds: Design Principles

Álvarez

Ruiz

2012

Supramolecular Chemistry

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The terminology and basic concepts of coordination chemistry are presented, in view of their potential application in the design of supramolecular systems based on transition metals. We describe the main features of the metal ions, mostly in relation to atomic size and oxidation state, and those of the ligands, such as denticity, topology, and flexibility. Polyhedra as stereochemical descriptors and the relationships of nested polyhedra are analyzed. The dependence of stereochemical preferences of the most common six‐ and four‐coordinate metal centers on the electron configuration is systematically studied, and a brief description of the common stereochemistries for other coordination numbers is presented. Finally, basic criteria for understanding the choice of coordination number by a particular combination of metal and ligands are discussed, and ways to describe the stereochemistries of coordination centers with ill‐defined coordination numbers are proposed.

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Gyroscopes and the chemical literature: 1852–2002

Cited by 90 publications

References 30 publications

Gyroscope like molecules consisting of trigonal or square planar osmium rotators within three-spoked dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties

Gyroscope like molecules consisting of trigonal or square planar osmium rotators within three-spoked dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties

Molecular machines operated by light

Self‐Assembly of Coordination Compounds: Design Principles

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