More Like this

1. Wire like diplatinum, triplatinum, and tetraplatinum complexes featuring X[PtCCCCCCCC] _m PtX segments; iterative syntheses and functionalization for measurements of single molecule properties

   https://doi.org/10.1039/C9DT00870E  

   Zheng, Qinglin; Schneider, Jakob F.; Amini, Hashem; Hampel, Frank; Gladysz, John A. (April 2019, Dalton Transactions)

   Reaction of ( p -tol 3 P) 2 PtCl 2 and Me 3 Sn(CC) 2 SiMe 3 (1 : 1/THF/reflux) gives monosubstituted trans -Cl( p -tol 3 P) 2 Pt(CC) 2 SiMe 3 (63%), which with wet n -Bu 4 N + F − yields trans -Cl( p -tol 3 P) 2 Pt(CC) 2 H ( 2 , 96%). Hay oxidative homocoupling (O 2 /CuCl/TMEDA) gives all- trans -Cl( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 Cl ( 3 , 68%). Reaction of 3 and Me 3 Sn(CC) 2 SiMe 3 (1 : 1/rt) affords monosubstituted all- trans -Cl( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 (46%), which is converted by a similar desilylation/homocoupling sequence to all- trans -Cl[( p -tol 3 P) 2 Pt(CC) 4 ] 3 Pt(P p -tol 3 ) 2 Cl ( 7 ; 79%). Reaction of ( p -tol 3 P) 2 PtCl 2 and excess H(CC) 2 SiMe 3 (HNEt 2 /cat. CuI) gives trans -Me 3 Si(CC) 2 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 (78%), which with wet n -Bu 4 N + F − affords trans -H(CC) 2 Pt(P p -tol 3 ) 2 (CC) 2 H (96%). Hay oxidative cross coupling with 2 (1 : 4) gives all- trans -Cl[( p -tol 3 P) 2 Pt(CC) 4 ] 2 Pt(P p -tol 3 ) 2 Cl ( 10 , 36%) along with homocoupling product 3 (33%). Reaction of 3 and Me 3 Sn(CC) 2 SiMe 3 (1 : 2/rt) yields all- trans -Me 3 Si(CC) 2 ( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 ( 17 , 77%), which with wet n -Bu 4 N + F − gives all- trans -H(CC) 2 ( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 H (96%). Reaction of 3 and excess Me 3 P gives all- trans -Cl(Me 3 P) 2 Pt(CC) 4 Pt(PMe 3 ) 2 Cl ( 4 , 86%). A model reaction of trans -( p -tol)( p -tol 3 P) 2 PtCl and KSAc yields trans -( p -tol)( p -tol 3 P) 2 PtSAc ( 12 , 75%). Similar reactions of 3 , 7 , 10 , and 4 give all- trans -AcS[(R 3 P) 2 Pt(CC) 4 ] n Pt(PR 3 ) 2 SAc (76–91%). The crystal structures of 3 , 17 , and 12 are determined. The first exhibits a chlorine–chlorine distance of 17.42 Å; those in 10 and 7 are estimated as 30.3 Å and 43.1 Å. 

   more » « less
2. En route to diplatinum polyynediyl complexes trans,trans-(Ar)(R3P)2Pt(C≡C)nPt(PR3)2(Ar): Untold tales, including end-group strategies

   https://doi.org/10.1351/pac200880030459  

   Stahl, Jürgen; Bohling, James C.; Peters, Thomas B.; de Quadras, Laura; Gladysz, John A. (January 2008, Pure and Applied Chemistry)

   Reactions of {(C 6 F 5 )Pt[S(CH 2 CH 2 -) 2 ](μ-Cl)} 2 and R 3 P yield the bis(phosphine) species trans -(C 6 F 5 )(R 3 P) 2 PtCl [R = Et ( Pt'Cl ), Ph, ( p -CF 3 C 6 H 4 ) 3 P; 88-81 %]. Additions of Pt'Cl and H(C≡C) n H ( n = 1, 2; HNEt 2 , 20 mol % CuI) give Pt'C 2 H (37 %, plus Pt'I , 16 %) and Pt'C 4 H (88 %). Homocoupling of Pt'C 4 H under Hay conditions (O 2 , CuCl, TMEDA, acetone) gives Pt'C 8 Pt' (85 %), but Pt'C 2 H affords only traces of Pt'C 4 Pt' . However, condensation of Pt'C 4 H and Pt'Cl (HNEt 2 , 20 mol % CuI) yields Pt'C 4 Pt' (97 %). Hay heterocouplings of Pt'C 4 H or trans -( p -tol)(Ph 3 P) 2 Pt(C≡C) 2 H ( Pt*C 4 H ) and excess HC≡CSiEt 3 give Pt'C 6 SiEt 3 (76 %) or Pt*C 6 SiEt 3 (89 %). The latter and wet n -Bu 4 N + F - react to yield labile Pt*C 6 H (60 %). Hay homocouplings of Pt*C 4 H and Pt*C 6 H give Pt*C 8 Pt* (64 %) and Pt*C 12 Pt* (64 %). Reaction of trans -(C 6 F 5 )( p -tol 3 P) 2 PtCl ( PtCl ) and HC≡CH (HNEt 2 , 20 mol % CuI) yields only traces of PtC 2 H . However, an analogous reaction with HC≡CSiMe 3 gives PtC 2 SiMe 3 (75 %), which upon treatment with silica yields PtC 2 H (77 %). An analogous coupling of trans -(C 6 F 5 )(Ph 3 P) 2 PtCl with H(C≡C) 2 H gives trans -(C 6 F 5 )(Ph 3 P) 2 Pt(C≡C) 2 H (34 %). Advantages and disadvantages of the various trans -(Ar)(R 3 P) 2 Pt end-groups are analyzed. 

   more » « less
3. Anthraquinone-based covalent organic framework as a recyclable direct hydrogen atom transfer photocatalyst for C–H functionalization

   https://doi.org/10.1039/d4sc00241e  

   Wang, Zitong; Yeary, Pierce; Fan, Yingjie; Lin, Wenbin (March 2024, Chemical Science)

   A COF-based catalyst was synthesized to activate C–H bonds for C–C/C–N coupling via hydrogen atom transfer. The catalyst can be easily recycled, allowing downstream modification of the product to realize C–H to C–N/C–S/C–O transformations. 

   more » « less
4. Global spectra of plant litter carbon, nitrogen and phosphorus concentrations and returning amounts

   https://doi.org/10.1111/1365-2745.14250  

   Yuan, Ji; Wu, Fuzhong; Peng, Changhui; Peñuelas, Josep; Vallicrosa, Helena; Sardans, Jordi; Peng, Yan; Wu, Qiqian; Li, Zimin; Heděnec, Petr; et al (April 2024, Journal of Ecology)

   Abstract Litter decomposition is a key ecological process that determines carbon (C) and nutrient cycling in terrestrial ecosystems. The initial concentrations of C and nutrients in litter play a critical role in this process, yet the global patterns of litter initial concentrations of C, nitrogen (N) and phosphorus (P) are poorly understood.We employed machine learning with a global database to quantitatively assess the global patterns and drivers of leaf litter initial C, N and P concentrations, as well as their returning amounts (i.e. amounts returned to soils).The medians of litter C, N and P concentrations were 46.7, 1.1, and 0.1%, respectively, and the medians of litter C, N and P returning amounts were 1.436, 0.038 and 0.004 Mg ha⁻¹ year⁻¹, respectively. Soil and climate emerged as the key predictors of leaf litter C, N and P concentrations. Predicted global maps showed that leaf litter N and P concentrations decreased with latitude, while C concentration exhibited an opposite pattern. Additionally, the returning amounts of leaf litter C, N and P all declined from the equator to the poles in both hemispheres.Synthesis: Our results provide a quantitative assessment of the global concentrations and returning amounts of leaf litter C, N and P, which showed new light on the role of leaf litter in global C and nutrients cycling. 

   more » « less
5. Carbon isotope trends across a century of herbarium specimens suggest CO ₂ fertilization of C ₄ grasses

   https://doi.org/10.1111/nph.19868  

   del_Toro, Isa; Case, Madelon_F; Tyler_Karp, A.; Slingsby, Jasper_A; Staver, A_Carla (May 2024, New Phytologist)

   Summary Increasing atmospheric CO₂is changing the dynamics of tropical savanna vegetation. C₃trees and grasses are known to experience CO₂fertilization, whereas responses to CO₂by C₄grasses are more ambiguous.Here, we sample stable carbon isotope trends in herbarium collections of South African C₄and C₃grasses to reconstruct¹³C discrimination.We found that C₃grasses showed no trends in¹³C discrimination over the past century but that C₄grasses increased their¹³C discrimination through time, especially since 1950. These changes were most strongly linked to changes in atmospheric CO₂rather than to trends in rainfall climatology or temperature.Combined with previously published evidence that grass biomass has increased in C₄‐dominated savannas, these trends suggest that increasing water‐use efficiency due to CO₂fertilization may be changing C₄plant–water relations. CO₂fertilization of C₄grasses may thus be a neglected pathway for anthropogenic global change in tropical savanna ecosystems. 

   more » « less