Reversible Coupling of Germylone with Isocyanates.

The germylone dimNHCGe (5, dimNHC=diimino N-heterocyclic carbene) undergoes a [2+2] cycloaddition with isocyanates RNCO (R=4-tolyl or 3,5-xylyl) to furnish novel alkyl carboxamido germylenes 7 (R=4-tolyl) and 8 (R=3,5-xylyl), featuring a C-C bond between the former carbene carbon and the isocyanate moiety. Heating a mixture of 8 with 4-tolyl isocyanate to 100 °C results in isocyanate metathesis, demonstrating reversible C-C bond formation on the reduced germanium compound. DFT calculations suggest that this process occurs via the reductive dissociation of isocyanate from 8 that regenerates the parent Ge(0) compound 5.

1,3-C-H bond activation on a transient gallium(I)/isocyanate adduct.

Reaction of NacNacGa with phenylisocyante generates a transient species amenable to unusual 1,3-C-H bond addition of unactivated sp3 C-H and sp2 C-H bonds of substrates featuring a hard donor atom. This reaction proceeds for pyridine oxide, dimethylsulfoxide, and dimethylacetamide, but not for pyridine, cyclohexanone, and ethyl acetate. C-H activation was also not observed for reactions with triethylphosphine oxide but, interestingly, in the presence of this compound isocyanate undergoes self-coupling on Ga(I) with a regioselectivity that is different when carried out in the absence of Et3PO.

A Guanidine-Supported π-Complex of Germanium Amenable to Intramolecular C-C Cleavage in Arene and Ge Atom Transfer.

The germylone dimNHCGe (dimNHC=diimino N-heterocyclic carbene) reacts with azides N3 R (R=SiMe3 or p-tolyl) to furnish the first examples of germanium π-complexes, i. e. guanidine-ligated compounds (dimNHI-SiMe3 )Ge (NHI=N-heterocyclic imine, R=SiMe3 ) and (dimNHI-Tol)Ge (R=p-tolyl). DFT calculations suggest that these species are formed by a Staudinger type replacement of dinitrogen in the azide by a nucleophilic germylone, leading to a transient carbene adduct of iminogermylidene. Heating a solution of compound (dimNHI-SiMe3 )Ge to 70 °C results in extrusion of the iminogermylidene that further aggregates to produce the known [Me3 SiNGe]4 tetramer, whereas the imidazolylidene fragment transforms into an unusual heptatriene species that can be considered as a product of carbene insertion into the C-C bond of a pendant Ar substituent at the imidazolylidene nitrogen of the dimNHC. Reaction of (dimNHI-SiMe3 )Ge with tetrachloro-o-benzoquinone results in the net transfer of a germanium atom and formation of the free diimino-guanidine ligand. This ligand also forms when (dimNHI-SiMe3 )Ge is treated with azide N3 (p-Tol), with the germanium product being [(p-Tol)NGe]n.

Germanium Analogue of the Parent Phosphine-Borane FLP Compound.

Diimino-carbene-supported germylone dimNHCGe does not react with BPh3 and does not activate dihydrogen in the FLP mode in the combination with this borane. However, it reacts with B(C6 F5 )3 to give the zwitterionic borate dimNHCGe-(C6 F4 )BF(C6 F5 )2 . This compound can be converted into the hydroborate dimNHCGe-(C6 F4 )BH(C6 F5 )2 (8) and further into [dimNHCGe-(C6 F4 )B(C6 F5 )2 ]+ (4). Compound 4 is a Ge/B analogue of Stephan's FLP parent P/B compound (C6 H2 Me3 )2 P-C6 F4 -B(C6 F5 )2 but unlike the latter cannot split dihydrogen. Moreover, attempts to prepare a Ge/B analogue of the zwitterion (C6 H2 Me3 )2 HP-C6 F4 -BH(C6 F5 )2 by protonation of borate 8 resulted in immediate elimination of H2.

Base-Stabilized Phosphinidene Oxide, Imide and Sulfide.

Oxidation of a base-stabilized phosphinidene (κ2 -NNP)P (12, NNP=phosphinoamidinate) with N2 O afforded a labile phosphinidene oxide (κ2 -NNP)P=O (16) which was characterized by NMR spectroscopy. Further oxidation of 16 by N2 O or reaction of 12 with two equivalents of pyridine oxide afforded the isolable dioxide (κ2 -NNP)PO2 which was characterized by NMR and SC XRD. Trapping of 16 with tolyl isocyanate resulted in P=O/N=C metathesis, eventually affording a urea-ligated phosphine (κ1 -NNP)P(NTol)2 C=O (17) The mechanism of this reaction was elucidated by DFT calculations. Reactions of phosphinidene 12 with azides generated transient imines (NNP)P=NR, which in the case of R=Tol underwent cycloaddition with tolyl Isocyanate to afford the urea product 17, and in the case of R=SiMe3 reacts with N3 SiMe3 via the addition of N-Si across the P=N bond affording, after the extrusion of dinitrogen, a P,N-heterocyclic compound. Both products of the reactions with azides have been fully characterized, both in solution and the solid-state. Finally, reaction of phosphinidene 12 with one equivalent of sulfur resulted in the isolation of the base-stabilized phosphinidene sulfide (κ2 -NNP)P=S that has also been fully characterized.

Small Molecule Activation on a Base-stabilized Phosphinidene.

Reduction of (NP)PCl2 (NP=phosphinoamidinate [PhC(NAr)(=NPPri 2 )]- ) with KC8 affords the phosphinoamidinato-supported phosphinidene (NP)P (9). Reaction of 9 with a N-heterocyclic carbene (MeC(NMe))2 C: results in the NHC-adduct NHC→P-P(Pri 2 )=NC(Ph)=NAr featuring an iminophosphinyl group. Reactions of 9 with HBpin and H3 SiPh led to the metathesis products (NP)Bpin and (NP)SiH2 Ph, respectively, whereas with HPPh2 a base-stabilized phosphido-phosphinidene, the product of N-P and H-P bond metathesis, was obtained. Reaction of 9 with tetrachlorobenzaquinone results in oxidation of P(I) to P(III), accompanied by oxidation of the amidophosphine ligand into P(V). Addition of benzaldehyde to 9 results in a phospha-Wittig reaction affording a product of P=P and C=O bond metathesis. Related reaction with phenylisocyanate results in a product of N-P(=O)Pri 2 addition to the C=N bond of an intermediate iminophosphaalkene to produce a phosphinidene intramolecularly stabilized by a diaminocarbene.

Synthesis and catalytic performance of nickel phosphinite pincer complexes in deoxygenative hydroboration of amides.

A series of imino-POCNR, amino-POCNR2, and bis(phosphinite) POCOP pincer complexes of Ni(II) were prepared and tested in catalytic deoxygenative hydroboration of amides with HBPin to the corresponding amines. In contrast to the deoxygenative hydrosilylation approach, primarily developed for tertiary amides, superior reactivity in Ni-catalyzed deoxygenative hydroboration was demonstrated for secondary carboxamides. The bis(phosphinite) hydride complex (POCOP)NiH proved the most active in these reactions, tolerating potentially reducible functionalities such as internal alkenes, esters, nitriles, heteroaromatic compounds, and tertiary amides. Preferable hydroboration of secondary amides was also demonstrated in the presence of primary amide functionalities. The reactions were conducted at 60-80 °C, representing a rare example of a base-metal catalytic system for selective deoxygenation of secondary amides to the corresponding amines under mild conditions. In contrast to secondary amides, deoxygenative hydroboration of primary amides was demonstrated using an iminophosphinite pre-catalyst (POCNDmp)Ni(CH2TMS) (Dmp = 2,6-Me2C6H3). Deoxygenation reactions were suggested to proceed via a direct C-O bond cleavage mechanism, which is triggered by dehydrogenative N-borylation to access more electrophilic N-borylamides amenable to the addition of HBPin to the carbonyl group.

The Insertion of EII and EIV Chlorides (E=Si, Ge) into the Si-Si Bond of Disilylene.

Reactions of silicon and germanium dichlorides L⋅ECl2 (E=Si, L=IPr; E=Ge, L=dioxane) with the phosphinoamidinato-supported disilylene ({κ2 (N,P)-NNP}Si)2 resulted in formal tetrylene insertions into the Si-Si bond. In the case of the reaction with silylene, two products were isolated. The first product ({κ2 (N,P)-NNP}Si)2 SiCl2 , is the formal product of direct SiCl2 insertion into the Si-Si bond of ({κ2 (N,P)-NNP}Si)2 and thus features two separated silylamido silylene centers. Over time, migration of the SiCl2 group to a lateral position afforded the second product, the disilylene {κ2 (Si,P)-SiCl2 NNP}Si-Si{κ2 (N,P)-NNP}. In contrast, insertion of GeCl2 resulted only in the isolation of the germanium analogue of {κ2 (Si,P)-SiCl2 NNP}Si-Si{κ2 (N,P)-NNP}, containing a Ge atom in the central position namely, compound {κ2 (Si,P)-SiCl2 NNP}Ge-Si{κ2 (N,P)-NNP}, which is a rare example of a silylene-germylene. Finally, reaction of disilylene ({κ2 (N,P)-NNP}Si)2 with SiCl4 and SiHCl3 led to the formation of the new bis(silyl)silylene, ({NNP}SiCl2 )2 Si:. All four new products from these insertion reactions have been characterized by multinuclear NMR and single-crystal X-ray diffraction studies.

The evolution of triphenylamine hole transport materials for efficient perovskite solar cells.

In recent years, the dramatic increase in power conversion efficiency (PCE) coupled with a decrease in the total cost of third-generation solar cells has led to a significant increase in the collaborative research efforts of academic and industrial researchers. Such interdisciplinary studies have afforded novel materials, which in many cases are now ready to be brought to the marketplace. Within this framework, the field of perovskite solar cells (PSCs) is currently an important area of research due to their extraordinary light-harvesting properties. In particular, PSCs prepared via facile synthetic procedures, containing hole transport materials (HTMs) with versatile triphenylamine (TPA) structural cores, amenable to functionalization, have become a focus of intense global research activity. To optimize the efficiency of the solar cells to achieve efficiencies closer to rival silicon-based technology, TPA building blocks must exhibit favourable electrochemical, photophysical, and photochemical properties that can be chemically tuned in a rational manner. Although PSCs based on TPA building blocks exhibit attractive properties such as high-power efficiencies, a reduction in their synthetic costs coupled with higher stabilities and environmental considerations still need to be addressed. Considering the above, a detailed summary of the most promising compounds and current methodologies employed to overcome the remaining challenges in this field is provided. The objective of this review is to provide guidance to readers on exploring new avenues for the discovery of efficient TPA derivatives, to aid in the future development and advancement of TPA-based PSCs for commercial applications.

Facile C-H bond activation on a transient gallium imide.

Reaction of NacNacGa with azide N3SiMe3 results in the generation of a transient imide NacNacGa(NSiMe3) that can cleave unactivated sp3 C-H and sp2 C-H bonds of different substrates, affording gallium amides. Pyridine, cyclohexanone, ethyl acetate, DMSO, and triethylphosphine oxide were activated in this process producing corresponding gallium amides. All new compounds were characterised by multinuclear NMR and X-ray diffraction.

An Isolable Gallium-Substituted Nitrilimine and its Reactivity with B-H, Si-H and B-B Bonds.

Reaction of the Ga(I) compound NacNacGa (9) with the diazo compound N2 CHSiMe3 affords the nitrilimine compound NacNacGa(N-NCSiMe3 )(CH2 SiMe3 ) (10). Carrying out this reaction in the presence of pyridine does not lead to C-H activation on the transient alkylidene NacNacGa=CHSiMe3 but generates a metallated diazo species NacNacGa(NHN=CHSiMe3 )(CN2 SiMe3 ) (13) that further rearranges into the isonitrile compound NacNacGa(NHN=CHSiMe3 )(N(NC)SiMe3 ) (15). Reactions of 10 with the silane H3 SiPh and the borane HBcat furnished products of 1,3 addition to the nitrilimine moiety NacNacGa{N(ERn )NCSiMe3 }(CH2 SiMe3 ), whereas reaction with the diborane B2 cat2 gave the product of formal nitrene insertion into the B-B bond. DFT calculations suggest that the interaction of 9 with N2 CHSiMe3 proceeds through intermediate formation of an alkylidene compound that undergoes CH activation with a second molecule of N2 CHSiMe3 . Insertion into the B-B bond likely proceeds through an initial 1,3-addition of the diborane, followed by boryl migration to the former nitrene center.

Two in One: A Dinuclear Ru(II) Complex for Deep-Red Light-Emitting Electrochemical Cells and as an Electrochemiluminescence Probe for Organophosphorus Pesticides.

The emissive properties of two Ru(II) complexes, [Ru(dmbipy)2L1][PF6]2 (1) and [Ru2(dmbipy)4L2][PF6]4 (2), (where L1 and L2 are π-extended phenanthroline-based ligands and dmbipy = 4,4'-dimethyl-2,2'-bipyridine) have been explored for dual applications, namely, deep-red light-emitting electrochemical cells (LECs) and electrochemiluminescence (ECL) sensors for the detection of organophosphorus pesticides (OPs) that include chlorpyrifos (CPS). A simple single-layer deep-red LEC device comprising 2 is reported that outperforms both its mononuclear derivative 1 and all previously reported dinuclear LECs, with a maximum brightness of 524 cd/m2, an external quantum efficiency of 0.62%, and a turn-on voltage of 3.2 V. Optoelectronic studies reveal that the ECL response of 2 is improved when compared to its mononuclear counterpart 1 and benchmark [Ru(bipy)3]2+ (3). Modified glassy carbon electrodes coated with 2 are highly sensitive deep-red ECL sensors that facilitate the detection of CPS directly from river water and fruit samples without any complex pretreatment steps, operating over a broad logarithmic concentration range, with a low detection limit.

Reactivity of a Phosphinoamidinate-Stabilized Disilylene toward H-X Bonds.

An efficient method for the preparation of a phosphinoamidinate-supported disilylene was developed, and its reactivity toward H-E bonds (E = elements from Groups 13-15) was studied. With HBpin, transfer of the ligand from silicon to boron was observed to afford (NP)Bpin. Reaction with a silane (H3SiPh) took place only at elevated temperatures, at which point oxidative addition of the N-P bond of the NP-ligand to one of the silicon atoms of the disilylene occurred prior to Si-H addition involving the remaining silylene center. In contrast, reaction of the disilylene with phosphine, HPPh2 furnished the phosphidosilylene (NP)SiPPh2 (16) together with a highly transient species that, on the basis of a trapping experiment with H3SiPh, is proposed to be the hydridosilylene (NP)SiH, 17. Interestingly, 16 reacts with HPPh2 to give the diphosphine (PPh2)2, most likely via a direct σ-bond metathesis process. The aforementioned products have been characterized by multinuclear NMR and single-crystal X-ray diffraction studies.

Selective Cross-Coupling of Unsaturated Substrates on AlI.

The AlI compound NacNacAl (1, NacNac = [ArNC(Me)CHC(Me)NAr]- , Ar = 2,6-iPr2 C6 H3 ) serves as a template for the chemoselective coupling between carbonyls (benzophenone, fenchone, isophorone, p-tolyl benzoate, N,N-dimethylbenzamide, (1-phenylethylidene)aniline) and pyridine. With the CH-acidic ketone (1R)-(+) camphor, the reaction affords a hydrido alkoxide compound of Al, formed as the result of enolization, whereas an enolizable imine, (1-phenylethylidene)aniline, and the bulky ketone isophorone, still chemoselectively couple with pyridine. In contrast, reaction with the ester p-tolyl benzoate results in cleavage of the ester bond together with replacement of the alkoxy group by a hydrogen atom of the pyridine moiety. This study demonstrates that for carbonyl substrates featuring phenyl substituents, the reaction proceeds via intermediate formation of η2 (C,X)-coordinated (X = O, N) carbonyl adducts, whereas the reaction of 1 with (R)-(-)-fenchone in the absence of pyridine leads to CH activation in the pendant isopropyl group of the Ar substituent of the NacNac ligand.

Synthesis, Study, and Application of Pd(II) Hydrazone Complexes as the Emissive Components of Single-Layer Light-Emitting Electrochemical Cells.

For the first time, square planar Pd(II) complexes of hydrazone ligands have been investigated as the emissive components of light-emitting electrochemical cells (LECs). The neutral transition metal complex, [Pd(L1)2]·2CH3OH (1), (HL1 = (E)-N'-(phenyl(pyridin-2-yl)methylene)isonicotinhydrazide), was prepared and structurally characterized. Complex 1 displays quasireversible redox properties and is emissive at room temperature in solution with a λmax of 590 nm. As a result, it was subsequently employed as the emissive material of a single-layer LEC with configuration FTO/1/Ga/In, where studies reveal that it has a yellow color with CIE(x, y) = (0.33, 0.55), a luminance of 134 cd cm-2, and a turn-on voltage of 3.5 V. Protonation of the pendant pyridine nitrogen atoms of L1 afforded a second ionic complex [Pd(L1H)2](ClO4)2 (2) which is also emissive at room temperature with a λmax of 611 nm, resulting in an orange LEC with CIE(x, y) = (0.43, 0.53). The presence of mobile anions and cations in the second inorganic transition metal complex resulted in more efficient charge injection and transport which significantly improved the luminance and turn-on voltage of the device to 188.6 cd cm-2 and 3 V, respectively. This study establishes Pd(II) hydrazone complexes as a new class of materials whose emissive properties can be chemically tuned and provides proof-of-concept for their use in LECs, opening up exciting new avenues for potential applications in the field of solid state lighting.

Control of Porphyrin Planarity and Aggregation by Covalent Capping: Bissilyloxy Porphyrin Silanes.

Porphyrins are cornerstone functional materials that are useful in a wide variety of settings, ranging from molecular electronics to biology and medicine. Their applications are often hindered, however, by poor solubilities that result from their extended, solvophobic aromatic surfaces. Attempts to counteract this problem by functionalizing their peripheries have been met with only limited success. Here, we demonstrate a versatile strategy to tune the physical and electronic properties of porphyrins using an axial functionalization approach. Porphyrin silanes (PorSils) and bissilyloxy PorSils (SOPS) are prepared from porphyrins by operationally simple κ4N-silylation protocols, introducing bulky silyloxy "caps" that are central and perpendicular to the planar porphyrin. While porphyrins typically form either J- or H-aggregates, SOPS do not self-associate in the same manner: the silyloxy axial substituents dramatically improve the solubility by inhibiting aggregation. Moreover, axial porphyrin functionalization offers convenient handles through which optical, electronic, and structural properties of the porphyrin core can be modulated. We observe that the identity of the silyloxy substituent impacts the degree of planarity of the porphyrin in the solid state as well as the redox potentials.

Oxidative addition of tetrathiocins to palladium(0) and platinum(0): a route to dithiolate coordination complexes.

The preparation of a series of 4,4',5,5'-substituted benzo-fused 1,2,5,6-tetrathiocins X2C6H2S4C6H2X2 (1a-1g) were prepared from the reaction of S2Cl2 with 1,2-C6H4X2 (X = OMe, OEt; X2 = OCH2O, OCH2CH2O, OCH2CH2CH2O, MeNC([double bond, length as m-dash]O)NMe, O(CH2CH2O)4). The oxidative addition of 1a-1g to zero-valent Pd2dba3 or Pt2dba3 (dba = dibenzylideneacetone) in the presence of bis (diphenylphosphino)ethane (dppe) resulted in formation of the substituted mononuclear benzenedithiolate complexes M(L)(dppe) [L = dithiolate ligand; 2a-2g (M = Pd) and 3a-3g (M = Pt)] in 37-89% yield based on recrystallized material. Representative examples of M(L)(dppf) [dppf = bis-diphenylphosphinoferrocene; 4a, 4g (M = Pd) and 5g (M = Pt)] were prepared in a similar fashion. The structures of all derivatives were determined by X-ray diffraction, multinuclear NMR and elemental analysis. The reactivity of the two crown ether dithiolate complexes, 2g and 4g, with 1 equivalent of NaBPh4 led to isolation of the 1 : 1 complexes in which the Na+ cation is bound in the macrocyclic crown, [Na(2g)(MeOH)2][BPh4] and [Na(4g)][BPh4] whose structures were determined by X-ray diffraction. Electrochemical studies supported through DFT calculations on the crown ether derivatives revealed a series of ligand-based oxidation waves corresponding to the dithiolate ligand (and dppf for 4g and 5g) whose redox potentials were shifted by ca. +0.1 V on binding to Na+.

Shedding Light on the Diverse Reactivity of NacNacAl with N-Heterocycles.

The aluminum(I) compound NacNacAl (NacNac=[ArNC(Me)CHC(Me)NAr]- , Ar=2,6-iPr2 C6 H3 , 1) shows diverse and substrate-controlled reactivity in reactions with N-heterocycles. 4-Dimethylaminopyridine (DMAP), a basic substrate in which the 4-position is blocked, induces rearrangement of NacNacAl by shifting a hydrogen atom from the methyl group of the NacNac backbone to the aluminum center. In contrast, C-H activation of the methyl group of 4-picoline takes place to produce a species with a reactive terminal methylene. Reaction of 1 with 3,5-lutidine results in the first example of an uncatalyzed, room-temperature cleavage of an sp2 C-H bond (in the 4-position) by an AlI species. Another reactivity mode was observed for quinoline, which undergoes 2,2'-coupling. Finally, the reaction of 1 with phthalazine produces the product of N-N bond cleavage.

Development of an Unsymmetrical Cyclopropenimine-Guanidine Platform for Accessing Strongly Basic Proton Sponges and Boron-Difluoride Diaminonaphthalene Fluorophores.

An unsymmetrical guanidine-cyclopropenimine proton sponge DAGUN and the related BF2 -chelate DAGBO are reported. Insight into the structural, electronic, bonding and photophysical properties of these two molecules are presented. Joint experimental and theoretical studies reveal the protonated form of DAGUN possesses an intramolecular N⋅⋅⋅H-N hydrogen bond which affords a high experimental pKBH+ of 26.6 (computed=26.3). Photophysical studies show that in solution DAGUN displays a green emission at 534 nm, with a large Stokes shift of 235 nm (14,718 cm-1 ). In contrast, the conjugate acid DAGUN-H+ is only weakly emissive due to attenuated intramolecular charge transfer. X-ray diffraction studies reveal that DAGBO contains a stable tetracoordinate boronium cation, reminiscent of the well-established BODIPY family of dyes. In solution, DAGBO exhibits a strong blue emission at 450 nm coupled with a large Stokes shift (Δλ=158 nm, Δν=11,957 cm-1 ) and quantum yield of 62 %, upon excitation at 293 nm. DAGBO sets the stage as the first entry into a new class of boron-difluoride diaminonaphthalenes (BOFDANs) that represent highly fluorescent and tunable next-generation dyes with future promise for biosensing and bioimaging applications.

Ge(0) Compound Stabilized by a Diimino-Carbene Ligand: Synthesis and Ambiphilic Reactivity.

The germylone dimNHCGe (5, dimNHC = diimino N-heterocyclic carbene) was successfully prepared via the reduction of the germanium cation [dimNHCGeCl]+ with KC8. The molecular structure of 5 was unambiguously established by both NMR spectroscopy and single-crystal X-ray diffraction. The reactivity of 5 was investigated, revealing that it undergoes oxidative addition of HCl, CH3I, and PhI, accompanied by an unusual migration of the H, Me, and Ph groups from germanium to the carbene ligand. Related chemistry was also observed with C5F5N, which results in the migration of the fluorinated pyridine moiety to the carbene ligand. Compound 5 also undergoes cycloaddition with tetrachloro-o-benzoquinone to afford a Ge(IV) adduct.