Living radical and cationic polymerizations in water and organic media

This lecture will focus two living polymerizations that can be carried out in water as well as in organic media. The first one is transition metal-catalyzed living radical polymerization, for which Ru(II) and other transition metals play a critical role to control the process; for aqueous systems, Ru(II) and Fe(II) half metallocene complexes are useful. The second is cationic polymerization with water-tolerant Lewis acids as catalysts, including rare earth triflates and boron trifluoride for selected monomers. Discussion will be directed to the design of initiating systems, search of versatile catalysts, and precision synthesis of new polymers.     

A neutral, monomeric germanium(I) radical

Stoichiometric reduction of the bulky β-diketiminato germanium(II) chloride complex [((But)Nacnac)GeCl] ((But)Nacnac = [{N(Dip)C(Bu(t))}(2)CH](-), Dip = C(6)H(3)Pr(i)(2)-2,6) with either sodium naphthalenide or the magnesium(I) dimer [{((Mes)Nacnac)Mg}(2)] ((Mes)Nacnac = [(MesNCMe)(2)CH](-), Mes = mesityl) afforded the radical complex [((But)Nacnac)Ge:](?) in moderate yields. X-ray crystallographic, EPR/ENDOR spectroscopic, computational, and reactivity studies revealed this to be the first authenticated monomeric, neutral germanium(I) radical.     

Reactions of collman complex with tin(IV) and germanium(IV) porphyris,formation of [tin(II) and germanium(II) porphyrins] tetracarbonyliron and crystal structure of [2,3,7,8,12,13,17,18-octaethylporphinato tin(II)] tetracarbonyliron

The action of Na₂Fe(CO)₄ with tin(IV) and germanium(IV) porphyrins affords metal(II) porphyrin complexes [(por)M(II)Fe(CO)₄] (por = porphyrinate, M - Sn(II) or Ge(II)). The molecular structure of [(oep)Sn(II)Fe(CO)₄] was solved by X-ray diffraction techniques. The molecular structure of [(oep)Sn(II)Fe(CO)₄] was solved by X-ray diffraction techniques : the Sn coordination is square pyramidal with the iron in axial position (Sn-Fe = 2.492(1)Å) whereas the Fe coordination is trigonal bipyramidal. Mössbauer parameters provide convincing evidence for the formal zero oxidation state of the iron atom.     

Synthesis and characterization of poly(phenylene oxide) graft copolymers by atom transfer radical polymerizations

A series of comb-like poly(phenylene oxide)s (PPO) graft copolymers with controlled grafting density and length of grafts were synthesized by atom transfer radical polymerization (ATRP). The α-bromo-poly(2,6-dimethyl-1,4-phenylene oxide)s (BPPO) were used as macroinitiators to polymerize vinyl monomers and the graft copolymers carrying polystyrene (PS), poly(p-acetoxystyrene) (PAS), and poly(methyl methacrylate) (PMMA) as side chains were synthesized and characterized by NMR, FTIR, GPC, DSC and TGA. The composition-dependent glass-transition temperatures (T_g) of PPO-g-PS exhibited good correlation with theoretical curve in Couchman equations except for the cases of low PS content (<40 mol%) copolymers in which a positive deviation was observed due to enhanced molecular interactions. The increase in monomer/initiator ratio led to the increase of degree of polymerization and the decrease of polydispersity. Despite the immiscibility nature between PPO and PMMA, the PPO-g-PMMA exhibited enhanced compatibilization as apparent single T_g in a wide temperature window throughout various compositions revealing an efficient segmental mixing on a molecular scale due to grafting structure.     

Mechanochemical Synthesis of Poly(germanium and tin organosiloxanes)

The mechanochemical reaction of polyphenylsiloxane with tin and germanium oxides gives rise to soluble tin and germanium phenylsiloxanes. Effect of the nature of the oxide and of the starting reagent ratio on the yield and composition of metal phenylsiloxanes was studied. The reaction products were studied by IR spectroscopy and X-ray phase analysis.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 610–613.Original Russian Text Copyright © 2005 by Kapustina, Shapkin, Ivanova, Lyakhina.     

Sustainable radical reduction through catalyzed hydrogen atom transfer reactions (CHAT-reactions)

A system with coupled catalytic cycles is described that allows radical reduction by catalyzed hydrogen atom transfer (CHAT) from transition metal hydrides. These intermediates are generated through H₂ activation. Radical generation is carried out by titanocene catalyzed electron transfer to epoxides. The reaction provides a novel entry into the atom-economical reduction of radicals that has long been considered as a critical issue for the industrial application of radical chemistry.     

New methods of synthesis of boron,germanium, and tin derivatives of pentavalent phosphorus thioacids

The reactions of S‐trimethylsilyl esters of S‐propyl‐4‐methoxyphenyltrithiophosphonic, bis(dialkylamido)dithiophosphoric, and S‐ethyl‐diethylamidotrithiophosphoric acids with trialkyl borates, triorganylbromogermanes, trimethyl(isobutylthio)germane, and trialkylchlorostannanes were studied. On the basis of these studies, new methods of synthesizing S‐boron, S‐germyl, and S‐stannyl derivatives of pentavalent phosphorus thioacids were developed. S‐Diethylaminomethyl O‐isopropyl‐4‐ethoxyphenyldithiophosphonate was obtained by the reaction of the diisopropylboron derivative of the corresponding dithiophosphonic acid with the aminal 6 . © 2002 John Wiley & Sons, Inc. Heteroatom Chem 13:27–35, 2002; DOI 10.1002/hc.1103     

Mass spectra of heteroaromatic derivatives of silicon,germanium, and tin (review)

A review summarizing material on the mass spectrometry of furyl and thienyl derivatives of the Group IVB elements.Dedicated to Professor A. R. Katritsky in connection with his 65th birthday.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, 891–898, July, 1993.     

Divalent silicon,germanium, and tin compounds with element--heteroatom bonds

Principal results and trends in chemistry of organic derivatives of divalent silicon, germanium, and tin containing bonds between these elements and the halogen, nitrogen, oxygen, and sulfur atoms are briefly surveyed. Selected characteristics of compounds with the element--phosphorus and element--arsenic bonds are discussed for comparison. Data on the synthesis and structures of new types of these compounds, viz., germanium(ii) diacylates, the alkoxy derivatives E¹⁴(OR)₂ and E¹⁴(OR)Y (E¹⁴ = Ge, Sn; R = Me₂NCH₂CH₂; Y = Cl, AcO, (Me₃Si)₂N), and the ate-complexes Li⁽⁺⁾[E¹⁴(OCH₂CH₂NMe₂)₃]^(–) and [Li(thf)₂]⁽⁺⁾[TsiE¹⁴(SBu)₂]^(–) (E¹⁴ = Ge, Sn; Tsi = (Me₃Si)₃C), are presented. It was established for the first time that germanium(ii) and tin(ii) derivatives can be stabilized in the monomeric form only through the intramolecular N_sp3E¹⁴ coordination bonds and the -acceptor effect of the oxygen atoms without introduction of bulky substituents.     

Fluorocarbon‐ended polymers: Metal catalyzed radical and living radical polymerizations initiated by perfluoroalkylsulfonyl halides

Perfluoroalkylsulfonyl chlorides and bromides initiate metal catalyzed free radical polymerization of both hydrocarbon and fluorocarbon monomers affording polymers with perfluoroalkyl end groups. In the case of styrene (S) and methyl methacrylate (MMA) with Cu‐based catalysts the process affords polymers with a relatively narrow molecular weight distribution and linear dependence of molecular weight on conversion, suggesting that a living radical polymerization mechanism occurs. The orders of reaction in monomer, initiator and catalyst for these polymerizations were determined. In the case of PMMA, the detailed structure of a perfluorobutane chain‐end was determined by NMR analysis. Perfluoroalkylsulfonyl chlorides are stable in neutral aqueous media. This permits their use as initators for fluoroolefin polymerizations in H₂O. Poly(tetrafluoroethylene‐co‐hexafluoropropylene) was obtained in good yield with few ionic end groups. The aqueous fluoroolefin polymerization appears to be catalyzed by metal zero species from the reactor walls. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3313–3335, 2000     

Cycloalkanes containing heterocyclic germanium,tin and lead

Treatment of the lithium reagent from 1,3-bis(trifluoromethyl)benzene (I) with carbon dioxide gave a 60/40 mixture of 2,4- and 2,6-bis(trifluoromethyl)-benzoic acids (IV) and (II). The lithiation/carbonation of 1,3-bis(trifluoromethyl)benzene-5-d (VIII) gave (II) and (IV) without loss of deutrium. This result indicates that (I), unlike trifluoromethylbenzene, does not lithiate meta to a CF₃ group.     

Controlling polymer structures by atom transfer radical polymerization and other controlled/living radical polymerizations

Fundamentals of controlled/living radical polymerization (CRP) and Atom Transfer Radical Polymerization (ATRP), relevant to the synthesis of controlled polymer structures are described. Macromolecular brushes with star like structure are used as an example to illustrate synthetic power of ATRP.     

Well-defined polyisocyanates via organotitanium(IV) catalyzed living polymerizations of isocyanates

The development of living organotitanium(IV) catalyzed polymerizations is presented. A living polymerization of alkyl isocyanates was developed using TiCl₃OCH₂CF₃, I, as a catalyst, through which large quantities of well-defined (in terms of molecular weight and polydispersity) polyisocyanates are obtainable under ambient conditions. η⁵-CpTiCl₂OCH₂CF₃ (Cp = cyclopentadienyl), II, is also an excellent catalyst for the polymerization of isocyanates and, unlike I, will polymerize monomers containing Lewis basic functional groups in the side chain. Compound II was used to synthesize poly(allyl isocyanate) and poly(2-isocyanatoethyl methacrylate). Both polymers were found to be soluble, in contrast to previous reports, and spectroscopic characterization showed that no crosslinking of the side chains had occurred.     

Synthesis, structure, and thermal properties of soluble hydrazinium germanium(IV) and tin(IV) selenide salts

The crystal structures of two hydrazinium-based germanium(IV) and tin(IV) selenide salts are determined. (N(2)H(5))(4)Ge(2)Se(6) (1) [I4(1)cd, a = 12.708(1) Angstroms, c = 21.955(2) Angstroms, Z = 8] and (N(2)H(4))(3)(N(2)H(5))(4)Sn(2)Se(6) (2) [P, a = 6.6475(6) Angstroms, b = 9.5474(9) Angstroms, c = 9.8830(10) Angstroms, alpha = 94.110(2) degrees, beta = 99.429(2) degrees, gamma = 104.141(2) degrees, Z = 1] each consist of anionic dimers of edge-sharing metal selenide tetrahedra, M(2)Se(6)(4-) (M = Ge or Sn), separated by hydrazinium cations and, for 2, additional neutral hydrazine molecules. Substantial hydrogen bonding exists among the hydrazine/hydrazinium molecules as well as between the hydrazinium cations and the selenide anions. Whereas the previously reported tin(IV) sulfide system, (N(2)H(5))(4)Sn(2)S(6), decomposes cleanly to microcrystalline SnS(2) when heated to 200 degrees C in an inert atmosphere, higher temperatures (>300 degrees C) are required to dissociate selenium from 1 and 2 for the analogous preparations of single-phase metal selenides. The metal chalcogenide salts are highly soluble in hydrazine, as well as in a variety of amines and DMSO, highlighting the potential usefulness of these compounds as precursors for the solution deposition of the corresponding metal chalcogenide films.     

Electron transfer. 144. Reductions with germanium(II)

Solutions 0.2-0.4 M in Ge(II) and 6 M in HCl, generated by reaction of Ge(IV) with H3PO2, are stable for more than 3 weeks and can be diluted 200-fold with dilute HCl to give GeCl3- preparations to be used in redox studies. Kinetic profiles for the reduction of Fe(III) by Ge(II), as catalyzed by Cu(II), implicate the odd-electron intermediate, Ge(III), which is formed from Cu(II) and Ge(II) (k = 30 M-1 s-1 in 0.5 M HCl at 24 degrees C) and which is consumed by reaction with Fe(III) (k = 6 x 10(2) M-1 s-1). A slower direct reaction between Ge(II) and Fe(III) (k = 0.66 M-1 s-1) can be detected in 1.0 M HCl. The reaction of Ge(II) with I3- in 0.01-0.50 M iodide is zero order in oxidant and appears to proceed via a rate-determining heterolysis of a Ge(II)-OH2 species (k = 0.045 s-1) which is subject to H(+)-catalysis. Reductions of IrCl6(2-) and PtCl6(2-) by Ge(II) are strongly Cl(-)-catalyzed. The Ir(IV) reaction proceeds through a pair of 1e- changes, of which the initial conversion to Ge(III) is rate-determining, whereas the Pt(IV) oxidant probably utilizes (at least in part) an inner-sphere PtIV-Cl-GeII bridge in which chlorine is transferred (as Cl+) from oxidant to reductant. The 2e- reagent, Ge(II), like its 5s2 counterpart, In(I), can partake in 1e- transactions, but requires more severe constraints: the coreagent must be more powerfully oxidizing and the reaction medium more halide-rich.     

Silicon,germanium, tin and lead analogues of acetylenes

Recent experimental results which have described the characterization of the first, stable heavier group 14 element analogues of acetylenes are outlined. It is shown that the use of large terphenyl substituents allows the isolation of transition metal-heavier group 14 element complexes that can achieve essential triple bonding by a three-fold orbital interaction between the transition metal and group 14 moiety. On the other hand the alkyne analogues RMMR (R = Ge, Sn or Pb) display increasing distortions from linearity to trans-bent geometry due to the accumulation of non-bonding electron density at the group 14 element. The non-bonding electron density comes at the expense of electron density in the bonding region between the group 14 elements. Accordingly the bond orders are decreased to values that are near double for the germanium and tin derivatives and single for the lead compound.     

The transfer of tin and germanium atoms from N-heterocyclic stannylenes and germylenes to diazadienes

New N-heterocyclic stannylenes and germylenes were synthesized by transamination of E[N(SiMe3)2] (E = Ge, Sn) with alpha-amino-aldimines or ethylidene-1,2-diamines and were characterized by spectroscopic methods and in the case of the germylene 10 g by X-ray diffraction. The reactions of several germylenes and stannylenes with diazadienes were studied by using dynamic NMR and computational methods. Experimental and theoretical studies confirmed that metathesis with exchange of the Group 14 atom is feasible for both stannylenes and germylenes, with exchange rates being generally higher for stannylenes. The metathesis of the diazadiene 3 b and the stannylene 1 b follows second-order kinetics and exhibits a sizeable negative entropy of activation. The transfer reaction is inhibited by bulky substituents in both reactants and surprisingly coincides with a suppression of the fragmentation of the stannylene into tin and diazadiene. A connection between oxidative addition and ring fragmentation was also observed in the reaction of 1 f with sulfur. Density functional theory (DFT) calculations suggest that all metathesis reactions proceed via transient spirocyclic [1+4] cycloaddition products, the formation of which is generally endothermic and endergonic. The spirostannanes display a distorted Psi-tbp geometry at the tin atom and their cycloreversion requires low or nearly negligible activation energies; spirogermanes exhibit distorted tetrahedral central atoms and sizeable energy barriers with respect to the same reaction. Complementary studies of cycloadditions of diazadienes to triplet germylenes or stannylenes indicate that these reactions are exothermic. The lowest triplet state in the carbene homologues results from promotion of an electron from an n(N) orbital with pi character rather than the n(C)-sigma orbital as in carbenes, and singlet-triplet excitation energies decrease from carbon to tin. Spirostannanes exhibit a triplet ground-state multiplicity that implies that the energy hypersurfaces for the reactions of singlet and triplet stannylenes with diazadienes intersect; for germylenes, the singlet hypersurface is always lower in energy. A reaction mechanism explaining the different thermal stabilities of N-heterocyclic germylenes and stannylenes, and the coincidence between ring metathesis and thermal decomposition of the latter, is proposed based on the different separation of the singlet and triplet energy hypersurfaces.