The syntheses and structural characterizations of the first extensive series of Group 9 (Co, Rh, and Ir) tricarbadecaboranyl halfsandwich complexes are reported. The carbonyl complexes 1,1-(CO) 2 -2-Ph-closo-1,2,3,4-MC 3 B 7 H 9 , M = Co (1), Rh (2), and 8,8,8-(CO) 3 -9-Phnido-8,7,9,10-IrC 3 B 7 H 9 (3) were obtained by the reactions of Li + (6-Phnido-5,6,9-C 3 B 7 H 9 ) − with Co(CO) 4 I, [Rh(CO) 2 Cl] 2 , and Ir(CO) 3 Cl, respectively. Further reactions of 1, 2, and 3 with 1,2-bis(diphenylphosphino)ethane (dppe) yielded the 1,1-dppe-2-Ph-closo-1,2,3,4-MC 3 B 7 H 9 , M = Co (4), Rh (5), and 8-CO-8,8-dppe-9-Ph-nido-8,7,9,10-IrC 3 B 7 H 9 (6) derivatives with their crystallographic determinations showing that 1 and 2 contain the η 6 -2-Ph-2,3,4-C 3 B 7 H 9 1− ligand with the metallatricarbadecaboranyl cluster fragments having closo-octadecahedral geometries, while 3 has a slipped-cage η 4 -9-Ph-7,9,10-C 3 B 7 H 9 1− coordination and a nido-cluster framework. The reaction of Li + (6-Ph-nido-5,6,9-C 3 B 7 H 9 ) − with [Rh(COD)Cl] 2 and [Ir(COD)Cl] 2 produced the COD coordinated complexes 1,1-COD-2-Ph-closo-1,2,3,4-MC 3 B 7 H 9 , M = Rh (7), Ir (8), with η 6 -2-Ph-2,3,4-C 3 B 7 H 9 1− ligands and closo-cluster structures. On the other hand, slipped-cage structures with η 4 -9-Ph-7,9,10-C 3 B 7 H 9 1− coordination were achieved by the reactions of 1, 3, or 8 with an excess of the stronger donor tert-butyl isocyanide to give 8,8,8-(CN t Bu) 3 -9-Ph-nido-8,7,9,10-MC 3 B 7 H 9 , M = Co (9), Ir (10), respectively, or by the reaction of 8 with 1 equiv of tert-butyl isocyanide to give 8,8-COD-8-CN t Bu-9-Ph-nido-8,7,9,10-IrC 3 B 7 H 9 (11). Upon the reaction of 1 with diphenylacetylene, both carbonyls were displaced with subsequent alkyne cyclization to form the tetraphenylcyclobutadienyl complex 1,1-(η 4 -C 4 Ph 4 )-2-Ph-closo-1,2,3,4-CoC 3 B 7 H 9 (12). The crystalline tetramethylcyclobutadienyl derivative 1,1-(η 4 -C 4 Me 4 )-2-Ph-closo-1,2,3,4-CoC 3 B 7 H 9 (13) was synthesized by the reaction of Li + (6-Ph-nido-5,6,9-C 3 B 7 H 9 ) − with (η 4 -C 4 Me 4 )Co(CO) 2 I, and its crystallographic determination confirmed the formation of a complex where a formal Co 3+ ion is sandwiched between η 4 -C 4 Me 4 2− and η 6 -2-Ph-2,3,4-C 3 B 7 H 9 1− ligands.In contrast to the reactions with diphenylacetylene, the reaction of 8 with 3-hexyne resulted in cage deboronation to produce 2,2-COD-10-Ph-closo-2,1,6,10-C 3 B 6 H 8 (14). Neither 7 nor 8 would undergo oxidativeaddition when treated with I 2 . Although 11 reacted with I 2 and perfluoro-1-iodohexane, oxidative-addition products were also not obtained, but instead, iodation of a cage boron occurred to produce 8,8-COD-1-CN t Bu-9-Ph-11-I-nido-8,7,9,10-IrC 3 B 7 H 8 (15).

Deboronation of the 11-vertex metallatricarbadecaboranes 1-(η5-C5H5)-2-Ph-closo-1,2,3,4-M-C3B7H9 [M = Ru, Fe] and 1,1,1-(CO)3-2-Ph-closo-1,2,3,4-M-C3B7H9 [M = Re] with tetrabutylammonium fluoride (TBAF) produced the first examples of the 10-vertex families of closo and nido metallatricarbanonaborane complexes, 2-(η5-C5H5)-10-Ph-closo-2,1,6,10-M-C3B6H8 [M = Ru (1), Fe (2)] and 5,5,5-(CO)3-10-Ph-nido-5,6,9,10-Re-C3B6H9– (3). Crystallographic characterizations of 1 and 3 confirmed geometries, based on a bicapped square antiprism for 1 and a bicapped square antiprism with one missing vertex for 3, that are consistent with their respective 22 (closo) and 24 (nido) skeletal-electron counts.

Brewer’s spent grain is the residue left after the separation of wort during the beer-brewing process. Although this by-product has been reported to have a high protein content, it is normally treated as waste. This work aims to isolate bioactive hydrolysates from BSG, and then explore their bioactivities. Two groups (A and B) of BSG were subjected to protein extraction using the alkaline extraction method at pH 12, where group A was pre-treated with cellulase, while group B was not pre-treated and was directly extracted. The final isolate yielded 50.18 ± 1.22% recovery of the BSGP from group A and 66.41 ± 0.37% recovery from group B. RP-HPLC profiles showed that the extracted BSGPs are mainly hydrophilic proteins. The proteins extracted by the two methods were hydrolyzed enzymatically using Alcalase and α-chymotrypsin. The hydrolysates obtained displayed blood pressure regulation activity and antioxidant properties, when assayed with angiotensin-converting enzyme assay, 2,2-diphenyl-picryl-hydrazyl assay, and ferric antioxidant power assay. It can be concluded that it is possible to extract good quality proteins from BSG and this by-product presents potential as a source for the extraction of a variety of proteins that might be of interest to the food industries.

A general method for the systematic syntheses of amino acid functionalized metallatricarbadecaboranyl complexes has been developed that employs the coppercatalyzed click addition reactions of N-azidoacetyl amino acid methyl esters to a p-ethynylphenyl substituent at a cage carbon of the metallatricarbadecaboranyl cage. The trimethylsilylprotected p-ethynylphenyl Li + [6-(p-((CH 3 ) 3 SiCC)C 6 H 4 )nido-5,6,9-C 3 B 7 H 9 − ] (1) tricarbadecaboranyl anion was synthesized via the reaction of arachno-4,6-C 2 B 7 H 12 − with p-((CH 3 ) 3 SiCC)C 6 H 5 CN. Reaction of 1 with (η 5 -C 5 H 5 )Fe(CO) 2 I and (η 5 -C 5 H 5 )Ru(CH 3 CN) 3 PF 6 produced 1-(η 5 -C 5 H 5 )-2-(p-((CH 3 ) 3 SiCC)C 6 H 4 )-closo-1,2,3,4-MC 3 B 7 H 9 (M = Fe (2), Ru (3)). Deprotection of 2 and 3 with K 2 CO 3 in MeOH/THF afforded the ethynyl derivatives 1-(η 5 -C 5 H 5 )-2-(p-(HCC)C 6 H 4 )-closo-1,2,3,4-MC 3 B 7 H 9 (M = Fe (4), Ru (5)). Click addition of the model compound benzyl azide to 4 and 5 to form the triazole complexes, 1-(η 5 -C 5 H 5 )-2-(p-(1-(C 6 H 5 CH 2 )-1H-1,2,3-N 3 C 2 -4-)C 6 H 4 )-closo-1,2,3,4-MC 3 B 7 H 9 (M = Fe (6), Ru (7)) confirmed the reactivity of the p-ethynyl group toward coppercatalyzed click azide addition, with the triazole-linked structure of 7 crystallographically established. Subsequent click addition reactions of the N-azidoacetyl amino acid methyl esters to 4 yielded a wide range of amino acid functionalized ferratricarbadecaboranyl complexes: 1-(η 5 -C 5 H 5 )-2-(p-(1-(Xaa-C(O)CH 2 )-1H-1,2,3-N 3 C 2 -4-)C 6 H 4 )-closo-1,2,3,4-FeC 3 B 7 H 9 (Xaa = PheOMe (8), LeuOMe (9), ValOMe (10), MetOMe (11), AlaOMe (12), TryOMe (13)).

A general method for the synthesis of cage-carbon-functionalized cyclopentadienyl iron and cyclopentadienyl ruthenium tricarbadecaboranyl complexes has been developed that employs palladium-catalyzed Sonogashira, Heck, and Stille cross-coupling reactions directed at a cage-carbon haloaryl substituent. The key Li(+)[6-(p-XC(6)H(4))-nido-5,6,9-C(3)B(7)H(9)(-)] (X = I (1), Br (2), Cl (3)) haloaryl-tricarbadecaboranyl anionic ligands were synthesized in high yields via the reaction of the arachno-4,6-C(2)B(7)H(12)(-) anion with the corresponding p-halobenzonitriles (p-XC(6)H(4)-CN). The reactions of the salts 1-3 with (η(5)-C(5)H(5))Fe(CO)(2)I and (η(5)-C(5)H(5))Ru(CH(3)CN)(3)PF(6) were then used to produce the haloaryl complexes 1-(η(5)-C(5)H(5))-2-(p-XC(6)H(4))-closo-1,2,3,4-MC(3)B(7)H(9) (M = Fe, X = I (4), Br (5), Cl (6) and M = Ru, X = I (7), Br (8), Cl (9)). The sonication-promoted Sonogashira coupling reactions of 4 with terminal alkynes catalyzed by Pd(dppf)(2)Cl(2)/CuI yielded the alkynyl-linked derivatives 1-(η(5)-C(5)H(5))-2-p-RC(6)H(4)-closo-1,2,3,4-FeC(3)B(7)H(9) (R = (PhC≡C)- (10), (CH(3)CH(2)C(O)OCH(2)C≡C)- (11), ((η(5)-C(5)H(5))Fe(η(5)-C(5)H(4)C≡C))- (12)). Heck reactions of 4 with terminal alkenes catalyzed by Pd(OAc)(2) yielded the alkene-functionalized products 1-(η(5)-C(5)H(5))-2-p-RC(6)H(4)-closo-1,2,3,4-FeC(3)B(7)H(9) (R = (PhCH(2)CH═CH)- (13), (CH(3)(CH(2))(2)CH═CH)- (14)), while the Stille cross-coupling reactions of 4 with organotin compounds catalyzed by Pd(PPh(3))(2)Cl(2) afforded the complexes 1-(η(5)-C(5)H(5))-2-p-RC(6)H(4)-closo-1,2,3,4-FeC(3)B(7)H(9) (R = Ph- (15), (CH(2)═CH)- (16), (CH(2)═CHCH(2))- (17)). These reactions thus provide facile and systematic access to a wide variety of new types of functionalized metallatricarbadecaboranyl complexes with substituents needed for potential metallocene-like biomedical and/or optoelectronic applications.