Objective To compare the total daily activity time, walking time and running time using food‐dispensing toys versus bowls in a group of client‐owned, primarily indoor dogs. Materials and Methods A two‐way, two period, randomised repeated measures mixed‐effects crossover study performed on 26 client‐owned, primarily indoor dogs. Results Toy feeding increased average daily total activity time by 12% and walking time by 26%. Average daily total activity time and walking time were reduced by 8 and 7% respectively with each increase in year of age. Gender, body condition and muscle condition had no significant effect on average daily total activity or walking time. Toy feeding, time, their interaction, age, gender, body condition and muscle condition had no significant effect on average daily running time. Clinical Significance Feeding toys may be helpful during weight loss programs to achieve the goal of increasing daily exercise duration in dogs that need to lose weight.
Chemistries of Nb(V) and Ta(V) compounds are essentially identical as a result of lanthanide contraction. Hydrolysis of M(NMe 2 ) 5 (M = Nb, Ta), for example, yields [M(μ 3 -O)(NMe 2 ) 3 ] 4 (M = Nb, 1; Ta, 2) reported earlier. The similar reactivities of Nb(V) and Ta(V) compounds make it challenging, for example, to separate the two metals from their minerals. We have found that the reactions of H 2 O with amide amidinates M(NMe 2 ) 4 [MeC(N i Pr) 2 ] (M = Nb, 3; Ta, 4) show that the niobium and tantalum analogues take different principal paths. For the Nb(V) complex 3, the amidinate and one amide ligand are liberated upon treatment with water, yielding [Nb(μ 3 -O)(NMe 2 ) 3 ] 4 (1). For the Ta(V) complex 4, the amide ligands are released in the reaction with H 2 O, leaving the amidinate ligand intact. [Ta(μ 3 -O)(NMe 2 ) 3 ] 4 (2), the analogue of 1, was not observed as a product in the reaction of 4 with H 2 O. To our knowledge, this is the first example of the formation of two different complexes that maintain the (V) oxidation state in both metals. The new complexes M(NMe 2 ) 4 [MeC(N i Pr) 2 ] (M = Nb, 3; Ta, 4) have been prepared by the aminolysis of M(NMe 2 ) 5 (M = Nb, Ta) with i PrN(H)C(Me)=N i Pr (5). The hydrolysis of 3 and 4 has been investigated by DFT electronic structure calculations. The first step in each hydrolysis reaction involves the formation of a hydrogen-bonded complex that facilitates a proton transfer to the amidinate ligand in 3 and protonation of an axial dimethylamide ligand in 4. Both proton transfers furnish an intermediate metal-hydroxide species. The atomic charges in 3 and 4 have been computed by Natural Population Analysis (NPA), and these data are discussed relative to which of the ancillary ligands is protonated initially in the hydrolysis sequence. Ligand exchanges in 3 and 4 as well as the exchange in i PrN(H)C(Me)=N i Pr (5) were probed by EXSY NMR spectroscopy, giving rate constants of the exchanges: 0.430(13) s −1 (3), 0.033(6) s −1 (4), and 2.23(7) s −1 (5), showing that the rate of the Nb complex Nb(NMe 2 ) 4 [MeC(N i Pr) 2 ] (3) is 13 times faster than that of its Ta analogue 4.
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