Synthesis of Soluble High Molar Mass Poly(Phenylene Methylene)-Based Polymers.

Poly(phenylene methylene) (PPM) is a multifunctional polymer that is also active as an anticorrosion fluorescent coating material. Although this polymer was synthesized already more than 100 years ago, a versatile synthetic route to obtain soluble high molar mass polymers based on PPM has yet to be achieved. In this article, the influence of bifunctional bis-chloromethyl durene (BCMD) as a branching agent in the synthesis of PPM is reported. The progress of the reaction was followed by gel permeation chromatography (GPC) and NMR analysis. PPM-based copolymers with the highest molar mass reported so far for this class of materials (up to Mn of 205,300 g mol-1) were isolated. The versatile approach of using BCMD was confirmed by employing different catalysts. Interestingly, thermal and optical characterization established that the branching process does not affect the thermoplastic behavior and the fluorescence of the material, thus opening up PPM-based compounds with high molar mass for applications.

Dioxygen Activation by a Bioinspired Tungsten(IV) Complex.

An increasing number of discovered tungstoenzymes raises interest in the biomimetic chemistry of tungsten complexes in oxidation states +IV, +V, and +VI. Bioinspired (sulfur-rich) tungsten(VI) dioxido complexes are relatively prevalent in literature. Still, their energetically demanding reduction directly correlates with a small number of known tungsten(IV) oxido complexes, whose chemistry is not well explored. In this paper, a reduction of the [WO2(6-MePyS)2] (6-MePyS = 6-methylpyridine-2-thiolate) complex with PMe3 to a phosphine-stabilized tungsten(IV) oxido complex [WO(6-MePyS)2(PMe3)2] is described. This tungsten(IV) complex partially releases one PMe3 ligand in solution, creating a vacant coordination site capable of activating dioxygen to form [WO2(6-MePyS)2] and OPMe3. Therefore, [WO2(6-MePyS)2] can be used as a catalyst for the aerobic oxidation of PMe3, rendering this complex a rare example of a tungsten system utilizing dioxygen in homogeneous catalysis. Additionally, the investigation of the reactivity of the tungsten(IV) oxido complex with acetylene, substrate of a tungstoenzyme acetylene hydratase (AH), revealed the formation of the tungsten(IV) acetylene adduct. Although this adduct was previously reported as an oxidation product of the tungsten(II) acetylene carbonyl complex, here it is obtained via substitution at the sulfur-rich tungsten(IV) center, mimicking the initial step of the first shell mechanism for AH as suggested by computational studies.

Molybdenum(VI) Bis(imido) Complexes: From Frustrated Lewis Pairs to Weakly Coordinating Cations.

Molybdenum(VI) bis(imido) complexes [Mo(NtBu)2 (LR )2 ] (R=H 1 a; R=CF3 1 b) combined with B(C6 F5 )3 (1 a/B(C6 F5 )3 , 1 b/B(C6 F5 )3 ) exhibit a frustrated Lewis pair (FLP) character that can heterolytically split H-H, Si-H and O-H bonds. Cleavage of H2 and Et3 SiH affords ion pairs [Mo(NtBu)(NHtBu)(LR )2 ][HB(C6 F5 )3 ] (R=H 2 a; R=CF3 2 b) composed of a Mo(VI) amido imido cation and a hydridoborate anion, while reaction with H2 O leads to [Mo(NtBu)(NHtBu)(LR )2 ][(HO)B(C6 F5 )3 ] (R=H 3 a; R=CF3 3 b). Ion pairs 2 a and 2 b are catalysts for the hydrosilylation of aldehydes with triethylsilane, with 2 b being more active than 2 a. Mechanistic elucidation revealed insertion of the aldehyde into the B-H bond of [HB(C6 F5 )3 ]- . We were able to isolate and fully characterize, including by single-crystal X-ray diffraction analysis, the inserted products Mo(NtBu)(NHtBu)(LR )2 ][{PhCH2 O}B(C6 F5 )3 ] (R=H 4 a; R=CF3 4 b). Catalysis occurs at [HB(C6 F5 )3 ]- while [Mo(NtBu)(NHtBu)(LR )2 ]+ (R=H or CF3 ) act as the cationic counterions. However, the striking difference in reactivity gives ample evidence that molybdenum cations behave as weakly coordinating cations (WCC).

New strategies towards advanced CT contrast agents. Development of neutral and monoanionic sulfur-bridged W(V) dimeric complexes.

Multinuclear tungsten complexes are intriguing candidates for new contrast media that can provide substantial improvements in CT imaging diagnostics. Herein, we present a ligand strategy, based on amino acids, and mono- and disubstituted EDTA derivatives, that enables the development of stable complexes with high tungsten content and reasonably low osmolality. Accordingly, a series of neutral and monoanionic di-µ-sulfido W(V) dimers have been synthesized via a convenient procedure utilizing microwave heating in combination with ion-pair HPLC reaction monitoring. The compounds were characterized in detail by various techniques, including ESI-HRMS, NMR spectroscopy, HPLC, elemental analysis, and X-ray crystallography. The aqueous stability of the complexes under physiologically relevant conditions, and during heat sterilization was also examined as an initial assessment of their potential applicability as radiocontrast agents. Monoanionic complexes featuring monosubstituted EDTA derivatives have demonstrated high stability, while producing a lower number of ions in solution (resulting in lower osmolality) in comparison to their bis-anionic EDTA counterparts. Nevertheless, they exhibited insufficient water solubility for application as intravascular contrast agents. However, our study showed that aqueous solubility of this type of complexes can be tuned by small modifications in the ligand structure.

Replacement of Molybdenum by Tungsten in a Biomimetic Complex Leads to an Increase in Oxygen Atom Transfer Catalytic Activity.

Upon replacement of molybdenum by tungsten in DMSO reductase isolated from the Rhodobacteraceae family, the derived enzyme catalyzes DMSO reduction faster. To better understand this behavior, we synthesized two tungsten(VI) dioxido complexes [WVIO2L2] with pyridine- (PyS) and pyrimidine-2-thiolate (PymS) ligands, isostructural to analogous molybdenum complexes we reported recently. Higher oxygen atom transfer (OAT) catalytic activity was observed with [WO2(PyS)2] compared to the Mo species, independent of whether PMe3 or PPh3 was used as the oxygen acceptor. [WVIO2L2] complexes undergo reduction with an excess of PMe3, yielding the tungsten(IV) oxido species [WOL2(PMe3)2], while with PPh3, no reactions are observed. Although OAT reactions from DMSO to phosphines are known for tungsten complexes, [WOL2(PMe3)2] are the first fully characterized phosphine-stabilized intermediates. By following the reaction of these reduced species with excess DMSO via UV-vis spectroscopy, we observed that tungsten compounds directly react to WVIO2 complexes while the Mo analogues first form µ-oxo Mo(V) dimers [Mo2O3L4]. Density functional theory calculations confirm that the oxygen atom abstraction from WVIO2 is an endergonic process contrasting the respective reaction with molybdenum. Here, we suggest that depending on the sacrificial oxygen acceptor, the tungsten complex may participate in catalysis either via a redox reaction or as an electrophile.

Synthesis and structure of two isomers of a molybdenum(II) 2-butyne complex stabilized by bioinspired S,N-bidentate ligands.

The synthesis and structural determination of two isomers of the molybdenum(II) complex (η2-but-2-yne)carbonylbis[2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)benzenethiolato-κ2N,S]molybdenum(II), [Mo(C11H12NOS)2(C4H6)(CO)] or Mo(CO)(C2Me2)(S-Phoz)2, are presented. The N,N-cis-S,S-trans isomer 1 shows quite different bond lengths to the metal atom [Mo-N = 2.4715 (10) versus 2.3404 (11) Å; Mo-S = 2.4673 (3) versus 2.3665 (3) Å]. In the N,N-trans-S,S-cis isomer 2, which is isotypic with the corresponding W complex, the Mo-N bond lengths [2.236 (2) and 2.203 (2) Å], as well as the Mo-S bond lengths [2.5254 (8) and 2.5297 (8) Å], are almost the same.

The Effect of Pyridine-2-thiolate Ligands on the Reactivity of Tungsten Complexes toward Oxidation and Acetylene Insertion.

Intending to deepen our understanding of tungsten acetylene (C2H2) chemistry, with regard to the tungstoenzyme acetylene hydratase, here we explore the structure and reactivity of a series of tungsten acetylene complexes, stabilized with pyridine-2-thiolate ligands featuring tungsten in both +II and +IV oxidation states. By varying the substitution of the pyridine-2-thiolate moiety with respect to steric and electronic properties, we examined the details and limits of the previously reported intramolecular nucleophilic attack on acetylene followed by the formation of acetylene inserted complexes. Here, we demonstrate that only the combination of high steric demand and electron-withdrawing features prevents acetylene insertion. Nevertheless, although variable synthetic approaches are necessary for their synthesis, tungsten acetylene complexes can be stabilized predictably with a variety of pyridine-2-thiolate ligands.

Synthesis and Reactivity of a Bioinspired Molybdenum(IV) Acetylene Complex.

The isolation of a molybdenum(IV) acetylene (C2H2) complex containing two bioinspired 6-methylpyridine-2-thiolate ligands is reported. The synthesis can be performed either by oxidation of a molybdenum(II) C2H2 complex or by substitution of a coordinated PMe3 by C2H2 on a molybdenum(IV) center. Both C2H2 complexes were characterized by spectroscopic means as well as by single-crystal X-ray diffraction. Furthermore, the reactivity of the coordinated C2H2 was investigated with regard to acetylene hydratase, one of two enzymes that accept C2H2 as a substrate. While the reaction with water resulted in the vinylation of the pyridine-2-thiolate ligands, an intermolecular nucleophilic attack on the coordinated C2H2 with the soft nucleophile PMe3 was observed to give a cationic ethenyl complex. A comparison with the tungsten analogues revealed less tightly bound C2H2 in the molybdenum variant, which, however, shows a higher reactivity toward nucleophiles.

Bioinspired Nucleophilic Attack on a Tungsten-Bound Acetylene: Formation of Cationic Carbyne and Alkenyl Complexes.

Inspired by the proposed inner-sphere mechanism of the tungstoenzyme acetylene hydratase, we have designed tungsten acetylene complexes and investigated their reactivity. Here, we report the first intermolecular nucleophilic attack on a tungsten-bound acetylene (C2H2) in bioinspired complexes employing 6-methylpyridine-2-thiolate ligands. By using PMe3 as a nucleophile, we isolated cationic carbyne and alkenyl complexes.

Vapochromism and Magnetochemical Switching of a Nickel(II) Paddlewheel Complex by Reversible NH3 Uptake and Release.

Reaction of [NiCl2 (PnH)4 ] (1) (PnH=6-tert-butyl-pyridazine-3-thione) with NiCl2 affords the binuclear paddlewheel (PW) complex [Ni2 (Pn)4 ] (2). Diamagnetic complex 2 is the first example of a PW complex capable of reversibly binding and releasing NH3 . The NH3 ligand in [Ni2 (Pn)4 (NH3 )] (2⋅NH3 ) enforces major spectroscopic and magnetic susceptibility changes, thus displaying vapochromic properties (λmax (2)=532 nm, λmax (2⋅NH3 )=518 nm) and magnetochemical switching (2: S=0; 2⋅NH3 : S=1). Upon repeated adsorption/desorption cycles of NH3 the PW core remains intact. Compound 2 can be embedded into thin polyurethane films (2P ) under retention of its sensing abilities. Therefore, 2 qualifies as reversible optical probe for ammonia. The magnetochemical switching of 2 and 2⋅NH3 was studied in detail by SQUID measurements showing that in 2⋅NH3 , solely the Ni atom coordinated the NH3 molecule is responsible for the paramagnetic behavior.

Hydroalkylation of Aryl Alkenes with Organohalides Catalyzed by Molybdenum Oxido Based Lewis Pairs.

Three molybdenum(VI) dioxido complexes [MoO2(L)2] bearing Schiff base ligands were reacted with B(C6F5)3 to afford the corresponding adducts [MoO{OB(C6F5)3}(L)2], which were fully characterized. They exhibit Frustrated Lewis-Pairs reactivity when reacting with silanes. Especially, the [MoO{OB(C6F5)3}(L)2] complex with L=2,4-dimethyl-6-((phenylimino)methyl)phenol proved to be active as catalyst for the hydroalkylation of aryl alkenes with organohalides and for the Atom-Transfer Radical Addition (ATRA) of organohalides to aliphatic alkenes. A series of gem-dichloride and gem-dibromide compounds with potential for further derivatization were synthesized from simple alkenes and organohalides, like chloroform or bromoform, using low catalyst loading.

Oxygen Atom Transfer Reactivity of Molybdenum(VI) Complexes Employing Pyrimidine- and Pyridine-2-thiolate Ligands.

Four dioxidomolybdenum(VI) complexes of the general structure [MoO2L2] employing the S,N-bidentate ligands pyrimidine-2-thiolate (PymS, 1), pyridine-2-thiolate (PyS, 2), 4-methylpyridine-2-thiolate (4-MePyS, 3) and 6-methylpyridine-2-thiolate (6-MePyS, 4) were synthesized and characterized by spectroscopic means and single-crystal X-ray diffraction analysis (2-4). Complexes 1-4 were reacted with PPh3 and PMe3, respectively, to investigate their oxygen atom transfer (OAT) reactivity and catalytic applicability. Reduction with PPh3 leads to symmetric molybdenum(V) dimers of the general structure [Mo2O3L4] (6-9). Kinetic studies showed that the OAT from [MoO2L2] to PPh3 is 5 times faster for the PymS system than for the PyS and 4-MePyS systems. The reaction of complexes 1-3 with PMe3 gives stable molybdenum(IV) complexes of the structure [MoOL2(PMe3)2] (10-12), while reduction of [MoO2(6-MePyS)2] (4) yields [MoO(6-MePyS)2(PMe3)] (13) with only one PMe3 coordinated to the metal center. The activity of complexes 1-4 in catalytic OAT reactions involving Me2SO and Ph2SO as oxygen donors and PPh3 as an oxygen acceptor has been investigated to assess the influence of the varied ligand frameworks on the OAT reaction rates. It was found that [MoO2(PymS)2] (1) and [MoO2(6-MePyS)2] (4) are similarly efficient catalysts, while complexes 2 and 3 are only moderately active. In the catalytic oxidation of PMe3 with Me2SO, complex 4 is the only efficient catalyst. Complexes 1-4 were also found to catalytically reduce NO3- with PPh3, although their reactivity is inhibited by further reduced species such as NO, as exemplified by the formation of the nitrosyl complex [Mo(NO)(PymS)3] (14), which was identified by single-crystal X-ray diffraction analysis. Computed ΔG⧧ values for the very first step of the OAT were found to be lower for complexes 1 and 4 than for 2 and 3, explaining the difference in catalytic reactivity between the two pairs and revealing the requirement for an electron-deficient ligand system.

Isomers in chlorido and alkoxido-substituted oxidorhenium(v) complexes: effects on catalytic epoxidation activity.

The syntheses and characterizations of oxidorhenium(v) complexes trans-dichlorido [ReOCl2(PPh3)(L1a)] (trans-2a), cis-dichlorido [ReOCl2(PPh3)(L1b)] (cis-2b) and ethoxido-complex [ReO(OEt)(L1b)2] (4b), ligated with the dimethyloxazoline-phenol ligands HL1a and HL1b are described. The bidentate ligand HL1a (2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-phenol) is unsubstituted on the phenol ring; ligand HL1b (2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-4-nitrophenol) contains a nitro group in para-position to the hydroxy group. In the reaction of precursor complex [ReOCl3(PPh3)2] and HL1a the two stereoisomers cis/trans-2a, with respect to chlorido ligands, are formed. The solid state structures of both isomers cis- and trans-2a were determined by single crystal X-ray diffraction analysis. In contrast, with ligand HL1b, only the cis-isomer cis-2b was obtained. Ethoxido-complex 4b is exclusively obtained when precursor [ReOCl3(OPPh3)(SMe2)] is reacted with 2 equiv. of HL1b in ethanol in the presence of the base 2,6-dimethylpyridine (lutidine). If no lutidine is added, chlorido-complex [ReOCl(L1b)2] (3b) is obtained. Complexes [ReOCl2(PPh3)(L1a)] (cis/trans-2a), [ReOCl2(PPh3)(L1b)] (cis-2b), [ReO(OMe)(L1a)2] (4a) and [ReO(OEt)(L1b)2] (4b) were tested as homogeneous catalysts in the benchmark reaction of cyclooctene epoxidation. The influence of isomerism and effects of ligand substitutions on catalytic activity was investigated. Based on the time-conversion plots it can be concluded that cis/trans-isomerism does not influence catalytic activity, but electron-withdrawing substituents, as in cis-2b, 3b and 4b, show a beneficial effect.

Soft Scorpionate Hydridotris(2-mercapto-1-methylimidazolyl) borate) Tungsten-Oxido and -Sulfido Complexes as Acetylene Hydratase Models.

A series of WIV alkyne complexes with the sulfur-rich ligand hydridotris(2-mercapto-1-methylimidazolyl) borate) (TmMe ) are presented as bio-inspired models to elucidate the mechanism of the tungstoenzyme acetylene hydratase (AH). The mono- and/or bis-alkyne precursors were reacted with NaTmMe and the resulting complexes [W(CO)(C2 R2 )(TmMe )Br] (R=H 1, Me 2) oxidized to the target [WE(C2 R2 )(TmMe )Br] (E=O, R=H 4, Me 5; E=S, R=H 6, Me 7) using pyridine-N-oxide and methylthiirane. Halide abstraction with TlOTf in MeCN gave the cationic complexes [WE(C2 R2 )(MeCN)(TmMe )](OTf) (E=CO, R=H 10, Me 11; E=O, R=H 12, Me 13; E=S, R=H 14, Me 15). Without MeCN, dinuclear complexes [W2 O(µ-O)(C2 Me2 )2 (TmMe )2 ](OTf)2 (8) and [W2 (µ-S)2 (C2 Me2 )(TmMe )2 ](OTf)2 (9) could be isolated showing distinct differences between the oxido and sulfido system with the latter exhibiting only one molecule of C2 Me2 . This provides evidence that a fine balance of the softness at W is important for acetylene coordination. Upon dissolving complex 8 in acetonitrile complex 13 is reconstituted in contrast to 9. All complexes exhibit the desired stability toward water and the observed effective coordination of the scorpionate ligand avoids decomposition to disulfide, an often-occurring reaction in sulfur ligand chemistry. Hence, the data presented here point toward a mechanism with a direct coordination of acetylene in the active site and provide the basis for further model chemistry for acetylene hydratase.

2H-[1,3]Thia-zolo[5,4,3-ij]quinolin-3-ium chloride monohydrate.

The structure of the title hydrated mol-ecular salt, C10H8NS+·Cl-·H2O, obtained by the reaction of sodium quinoline-8-thiolate Na(Quin-8-S) with CH2Cl2 and an aqueous solution of [Bu4N]Cl, contains π-stacked cations [plane-to-plane separation = 3.338 (4)-3.356 (4) Å] and features chains built by alternating Cl- anions and H2O mol-ecules connected by O-H⋯O hydrogen bonds. The cation shows whole-mol-ecule disorder over two flipped orientations in a 0.853 (3):0.147 (3) ratio.

Structural Mimics of Acetylene Hydratase: Tungsten Complexes Capable of Intramolecular Nucleophilic Attack on Acetylene.

Bioinspired complexes employing the ligands 6-tert-butylpyridazine-3-thione (SPn) and pyridine-2-thione (SPy) were synthesized and fully characterized to mimic the tungstoenzyme acetylene hydratase (AH). The complexes [W(CO)(C2 H2 )(CHCH-SPy)(SPy)] (4) and [W(CO)(C2 H2 )(CHCH-SPn)(SPn)] (5) were formed by intramolecular nucleophilic attack of the nitrogen donors of the ligand on the coordinated C2 H2 molecule. Labelling experiments using C2 D2 with the SPy system revealed the insertion reaction proceeding via a bis-acetylene intermediate. The starting complex [W(CO)(C2 H2 )(SPy)2 ] (6) for these studies was accessed by the new acetylene precursor mixture [W(CO)(C2 H2 )n (MeCN)3-n Br2 ] (n=1 and 2; 7). All complexes represent rare examples in the field of W-C2 H2 chemistry with 4 and 5 being the first of their kind. In the ongoing debate on the enzymatic mechanism, the findings support activation of acetylene by the tungsten center.

Bioinspired models for an unusual 3-histidine motif of diketone dioxygenase enzyme.

Bioinspired models for contrasting the electronic nature of neutral tris-histidine with the anionic 2-histidine-1-carboxylate facial motif and their subsequent impact on catalysis are reported. Herewith, iron(ii) complexes [Fe(L)(CH3CN)3](SO3CF3)21-3 of tris(2-pyridyl)-based ligands (L) have been synthesized and characterized as accurate structural models for the neutral 3-histidine triad of the enzyme diketone dioxygenase (DKDO). The molecular structure of one of the complexes exhibits octahedral coordination geometry and Fe-N11py bond lengths [1.952(4) to 1.959(4) Å] close to the Fe-NHis bond distances (1.98 Å) of the 3-His triad in the resting state of the enzyme, as obtained by EXAFS studies. The diketonate substrate-adduct complexes [Fe(L)(acacR)](SO3CF3) (R = Me, Ph) of 1-3 have been obtained using Na(acacR) in acetonitrile. The Fe2+/3+ redox potentials of the complexes (1.05 to 1.2 V vs. Fc/Fc+) and their substrate adducts (1.02 to 1.19 V vs. Fc/Fc+) appeared at almost the same redox barrier. All diketonate adducts exhibit two Fe(ii) → acac MLCT bands around 338 to 348 and 430 to 490 nm. Exposure of these adducts to O2 results in the decay of both MLCT bands with a rate of (kO2) 5.37 to 9.41 × 10-3 M-1 s-1. The kO2 values were concomitantly accelerated 20 to 50 fold by the addition of H+ (acetic acid), which nicely models the rate enhancement in the enzyme kinetics by the glutamate residue (Glu98). The oxygenation of the phenyl-substituted adducts yielded benzoin and benzoic acid (40% to 71%) as cleavage products in the presence of H+ ions. Isotope-labeling experiments using 18O2 showed 47% incorporation of 18O in benzoic acid, which reveals that the oxygen originates from dioxygen. Thus, the present model complexes exhibit very similar chemical surroundings to the active site of DKDO and mimic its functions elegantly. On the basis of these results, the C-C bond cleavage reaction mechanism is discussed.

Bioinspired Tungsten Complexes Employing a Thioether Scorpionate Ligand.

The synthesis and characterization of a series of novel tungsten complexes employing the bioinspired, sulfur-rich scorpionate ligand [PhTt] (phenyltris((methylthio)methyl)borate) are reported. Starting from the previously published tungsten precursor [WBr2(CO)3(NCMe)2], a salt metathesis reaction with 1 equiv of Cs[PhTt] led to the desired complex [WBr(CO)3(PhTt)] (1), making it the first tungsten complex employing a poly(thioether)borate ligand. Surprisingly, the reaction of [WBr2(CO)3(NCMe)2] with an excess of the ligand gave complex [W(CO)2(η2-CH2SMe)(PhTt)] (2) with a bidentate (methylthio)methanide ligand as the major product. Thereby, phenyldi((methylthio)methyl)borane is formed, which was isolated and characterized by NMR spectroscopy. The bromido ligand in [WBr(CO)3(PhTt)] was further substituted by the S,N-bidentate methimazole in order to make the first coordination sphere more sulfur-rich forming [W(CO)2(mt)(PhTt)] (3). Alkyne tungsten complexes employing the sulfur-rich scorpionate ligand were accessible by reaction of [WBr2(CO)(C2R2)2(NCMe)] (R = Me, Ph) with Cs[PhTt] forming [WBr(CO)(C2R2)2(PhTt- S, S')] (R = Me 4, Ph 5), with the potentially tridentate ligand coordinated only via two sulfur atoms. In the case of 4, the higher flexibility of the bidentate coordination leads to the formation of two isomers with respect to the six-membered ring formed by the tungsten center and the two coordinated sulfur atoms of the ligand. All complexes 1-5 were characterized by single-crystal X-ray diffraction analysis.

Dioxygen Activation with Molybdenum Complexes Bearing Amide-Functionalized Iminophenolate Ligands.

Two novel iminophenolate ligands with amidopropyl side chains (HL2 and HL3) on the imine functionality have been synthesized in order to prepare dioxidomolybdenum(VI) complexes of the general structure [MoO2L2] featuring pendant internal hydrogen bond donors. For reasons of comparison, a previously published complex featuring n-butyl side chains (L1) was included in the investigation. Three complexes (1-3) obtained using these ligands (HL1-HL3) were able to activate dioxygen in an in situ approach: The intermediate molybdenum(IV) species [MoO(PMe3)L2] is first generated by treatment with an excess of PMe3. Subsequent reaction with dioxygen leads to oxido peroxido complexes of the structure [MoO(O2)L2]. For the complex employing the ligand with the n-butyl side chain, the isolation of the oxidomolybdenum(IV) phosphino complex [MoO(PMe3)(L1)2] (4) was successful, whereas the respective Mo(IV) species employing the ligands with the amidopropyl side chains were found to be not stable enough to be isolated. The three oxido peroxido complexes of the structure [MoO(O2)L2] (9-11) were systematically compared to assess the influence of internal hydrogen bonds on the geometry as well as the catalytic activity in aerobic oxidation. All complexes were characterized by spectroscopic means. Furthermore, molecular structures were determined by single-crystal X-ray diffraction analyses of HL3, 1-3, 9-11 together with three polynuclear products {[MoO(L2)2]2(µ-O)} (7), {[MoO(L2)]4(µ-O)6} (8) and [C9H13N2O]4[Mo8O26]·6OPMe3 (12) which were obtained during the synthesis of reduced complexes of the type [MoO(PMe3)L2] (4-6).

Interaction of Metal Oxido Compounds with B(C6 F5 )3.

Lewis acid-base pair chemistry has been placed on a new level with the discovery that adduct formation between an electron donor (Lewis base) and acceptor (Lewis acid) can be inhibited by the introduction of steric demand, thus preserving the reactivity of both Lewis centers, resulting in highly unusual chemistry. Some of these highly versatile frustrated Lewis pairs (FLP) are capable of splitting a variety of small molecules, such as dihydrogen, in a heterolytic and even catalytic manner. This is in sharp contrast to classical reactions where the inert substrate must be activated by a metal-based catalyst. Very recently, research has emerged combining the two concepts, namely the formation of FLPs in which a metal compound represents the Lewis base, allowing for novel chemistry by using the heterolytic splitting power of both together with the redox reactivity of the metal. Such reactivity is not restricted to the metal center itself being a Lewis acid or base, also ancillary ligands can be used as part of the Lewis pair, still with the benefit of the redox-active metal center nearby. This Minireview is designed to highlight the novel reactions arising from the combination of metal oxido transition-metal or rare-earth-metal compounds with the Lewis acid B(C6 F5 )3 . It covers a wide area of chemistry including small molecule activation, hydrogenation and hydrosilylation catalysis, and olefin metathesis, substantiating the broad influence of the novel concept. Future goals of this young and exciting area are briefly discussed.